Rotaxanes Review PDF

Review
pubs.acs.org/CR
Development of Pseudorotaxanes and Rotaxanes: From Synthesis to

Stimuli-Responsive Motions to Applications
Min Xue, Yong Yang, Xiaodong Chi, Xuzhou Yan, and Feihe Huang*,
State Key Laboratory of Chemical Engineering, Center for Chemistry of High-Performance & Novel Materials, Department of
Chemistry, Zhejiang University, Hangzhou 310027, Peoples Republic of China
Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou 310018, Peoples Republic of China
2.11. Rotaxane-Related HostGuest Complexes
Based on Molecular Tweezers and Clips
3. Stimuli-Responsive Molecular Mobility of Pseudorotaxanes
3.1. Association/Dissociation Mobility
3.1.1. Solvent Eects on Association Constants
3.1.2. Temperature Eect: Slippage or Deslippage?
3.1.3. External Stimuli
3.2. Shuttling Mobility
3.3. Functions of Pseudorotaxanes
3.3.1. Fluorescent Sensors
3.3.2. Molecular Logic Gates
3.3.3. Molecular Switches
3.3.4. Other Molecular Machines
4. Stimuli-Responsive Molecular Mobility of Rotaxanes
4.1. Rotational Mobility
4.2.1. Observation of Shuttling and Its Dynamic Control
4.2.2. Stimuli-Responsive Molecular Shuttles
4.2.3. Modulating Properties and Functions of
Molecular Shuttles
4.3. Mobility of [c2]Daisy Chains
5. Applications of Pseudorotaxanes and Rotaxanes
5.1. Protection of Encapsulated Molecules
5.1.1. Unstable Species
5.1.2. Dyes
5.2. Stimuli-Responsive Supramolecular Polymeric Materials
5.3. Applications of Rotaxane-Based Molecular
Machines
5.3.1. Molecular Electronic Devices Based on
the LangmuirBlodgett Monolayers
5.3.2. Rotaxane-Based Molecular Machines on
Surfaces
5.4. MetalOrganic Frameworks
6. Conclusions and Future Perspectives
Author Information
Corresponding Author
Notes
CONTENTS
1. Introduction
2. Synthesis of Rotaxanes Based on Various Macrocycles
2.1. Crown Ethers
2.1.1. Bis(m-phenylene)-32-crown-10 and
Crown Ethers with Larger Sizes
2.1.2. Dibenzo-24-crown-8
2.1.3. Benzo-21-crown-7
2.1.4. Crown Ether-Based Cryptands
2.2. Cyclodextrins
2.3. Cucurbiturils
2.3.1. Cucurbit[6]uril
2.4. Calixarenes
2.4.1. Calix[4]arenes as Linkers or Stoppers
2.4.2. Calix[5]arenes and Calix[6]arenes as
Wheels
2.4.3. Heterocalix[n]arenes or Calix[n]heteroarenes
2.5. Pillararenes
2.5.1. Organic Solvent-Soluble Pillararenes
2.5.2. Water-Soluble Pillararenes
2.6. Tetracationic Cyclophanes
2.7. Amide-Based Macrocycles
2.7.1. Tetralactam Macrocycles with Diarylmethane Motif
2.7.2. Tetralactam Macrocycles with Benzylamide Motif
2.7.3. Other Lactam Macrocycles
2.8. Coordination-Based Macrocycles
2.9. Synthesis of Oligorotaxanes
2.10. Isomeric Rotaxanes
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Special Issue: 2015 Supramolecular Chemistry

Received: October 10, 2014
Published: March 3, 2015
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Chemical Reviews
Biographies
Acknowledgments
References
Review
Furthermore, the most popular and eective click chemistry

has also been widely exploited for the rotaxane synthesis.15 This
breakthrough in synthesis makes these compounds more
accessible, and allows the introduction of various functional
groups into their backbones and more complexity in their
structures. System complexity ranges from simple [1]rotaxanes16 or [2]rotaxanes17 to daisy chains,18 oligorotaxanes,19 and even to polyrotaxanes (Figure 2).20 With the
unique encapsulated structural features, rotaxanes have found
applications in the modication of physical and chemical
properties of guest molecules,21 and protection of substrates
such as dyes from chemical attack and aggregation.22
The interest in these supramolecular architectures came rst
from their beautiful interlocked structures, but was further
developed due to their unique mobile features, which resulted
from the high degree of freedom among the relatively
independent rod or linear components. Control of mobilities
can be achieved by some chemical or physical stimuli, such as
acid/base, anion, cation, photochemistry, and electrochemistry.
For pseudorotaxanes, there mainly exists the mobility of
association and dissociation, as well as the shuttling motion of
the wheels on unstoppered linear units in a few examples. On
the basis of the dynamic property of association and
dissociation, pseudorotaxanes can be endowed with the
functions of control/release and lock/key. It allows them to
be applied in the construction of various molecular devices such
as switches,23,24 logic gates,25 sensors,26 and nanovalves.27 For
rotaxanes, two types of motions, rotating and shuttling of the
macrocycles around the axles, are involved. Since the mobility
of rotaxanes was observed, intensive investigations from
controlling the mobile rate,28 or even stopping its behavior,29
to manipulating its motion at will via external stimuli30 have
been devoted to this eld. Stimuli-responsive molecular shuttles
provide rotaxanes with a promising basis for articial molecular
machines, such as nanomotors,31 elevators,32 or molecular
rachets.33 Among dierent types of rotaxanes, daisy chains,
because of their unique muscle-like mobility, have gained
special attention.18
Besides the various forms of motions in solution, rotaxanes
have also been prepared in the solid state,34 on surfaces,35 or as
a part of metalorganic frameworks (MOFs).36 The transfer of
molecular-machine technology into solid substrates is a key
step for the development of many potential applications of
rotaxanes as smart materials with switchable properties in
molecular electronics and other types of molecular machinery.37 Specially rotaxane-incorporated metalorganic frameworks as a new perspective for rotaxanes, giving up their
disadvantage of random motion in solution, have achieved a
higher level of molecular organization and provided a platform
for coherent switching between their mounted components.38
By incorporating pseudorotaxane or rotaxane moieties into
polymers, polypseudorotaxanes and polyrotaxanes can be
constructed in various types.39 On the other hand, pseudorotaxanes or rotaxanes can also be employed to self-assemble
into supramolecular polymers through noncovalent interactions.40,41 Because of their convenient environmental-responsiveness and reversible nature, these supramolecular systems
have novel applications in the fabrication of polymeric materials
such as hydrogels, molecular muscles, nanoparticles, and
micelles.42 The stimuli-responsive supramolecular polymeric
materials have been investigated for biomedical and pharmaceutical applications in recent years, which have a strong impact
on materials science accordingly.43,44
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1. INTRODUCTION
The history of isomeric types of organic molecules has passed
through several important stages: (1) Molecules that dier
from each other with dierent numbers and types of atoms; (2)
constitutional isomers with typical sequence and nature of
bonding between these atoms; (3) stereoisomers that are
distinguished by the spatial arrangement around an atom or
center; and (4) topological isomers with distinct topological
geometries. It is the last form of isomerism that leads to
mechanically interlocked molecules (MIMs), such as catenanes,
rotaxanes, and knots, which gain their inspiration from various
natural objects and architectures.15 Chemists have paid
attention to making MIMs for more than 50 years, not only
because of their aesthetic beauty but also due to their potential
applications as molecular devices for information storage and
processing, etc.6 As one type of interlocked molecules, the
rotaxane architecture is considered as a versatile platform to
construct functional articial nanomachines.7
Rotaxane is derived from the Latin words for wheel and
axle, and describes a compound that consists of a linear
species (sometimes called the rodlike part or guest) and cyclic
species (sometimes called the beadlike part or host) bound
together in a threaded structure by noncovalent forces.
Pseudo means false, so pseudorotaxane without bulky
stoppers at the end of the axle means false rotaxane, which is
actually a supramolecular complex but not a compound.
Sometimes a pseudorotaxane with only one stopper is called
semirotaxane. Cartoon representations of pseudorotaxane,
semirotaxane, and rotaxane are shown in Figure 1. The gray
balls here represent stoppers, which are bulky groups and can
prevent dethreading of the cyclic component.
Figure 1. Cartoon representations of pseudorotaxane, semirotaxane,

and rotaxane.
The strategies for the synthesis of rotaxanes developed from

statistical threading to directed template synthesis.8,9 The
statistical threading method (Scheme 1) was originally
introduced by Harrison and co-workers in 1967.8 The
formation of pseudorotaxanes and rotaxanes by this method
is based on a purely statistical progress without any apparent
attractive force between the linear species and the cyclic
molecules. In the course of the past 30 years, rotaxanes have
been easily accessed via template methods9 derived from
stacking interactions,10 hydrogen bonding,11 hydrophobic
interactions,12 metal ion coordination,13 and anion templates.14
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Scheme 1. First Synthesis of a [2]Rotaxane by the Statistical Threading Method
Scheme 2. General Approaches to the Construction of

Rotaxanes
Figure 2. Cartoon representations of dierent types of rotaxanes.
Up to now, rotaxane-based chemistry has been developed to

a giant research area with various ne branches, such as
template synthesis of rotaxanes,9,45 porphyrin rotaxanes,46
dendrimer rotaxanes,47 metal-directed synthesis of rotaxanes,48
pH-driven rotaxanes,49 rotaxane-based molecular machines,50
and so on. Each branch can be treated as a topic of study. In
this Review, we will mostly describe the chemistry of rotaxanes
in the last 10 years in a historical development order. In the rst
section, the synthesis of rotaxanes will be presented. These
rotaxanes will be divided into dierent types based on the
macrocycles incorporated in them, such as crown ethers,
cyclodextrins, cucurbiturils, calixarenes, pillararenes, cyclobis(paraquat-p-phenylene), amide macrocycles, and coordinationbased macrocycles. The mobility and external stimuliresponsive properties of pseudorotaxanes and rotaxanes then
will be discussed, respectively, followed by potential applications and perspectives on these mobile molecules. Polypseudorotaxanes and polyrotaxanes will not be included here. Up to
now, more than 6000 papers have been published on
pseudorotaxanes and/or rotaxanes. It is almost impossible for
us to cite all of them in this Review. We must say sorry to
those authors whose papers on pseudorotaxanes and/or
rotaxanes are not cited here.
capping the thread with bulky groups to prevent it from

dethreading.52 A similar route is snapping, in which the axle
containing an end group allows threading by the cyclic bead
(yielding a semirotaxane), and then bears another end group.53
This method is often used to prepare nonsymmetric rotaxanes.
When the macrocycle is formed around the linear part of the
dumbbell-like unit, it is called clipping.54 However, in a slipping
route, the cyclic molecule can thread over a blocking group of
the dumbbell-like unit at elevated temperatures.55 In Scheme
2e, active metal template strategy is described, in which the
metal plays a dual role in gathering and positioning of the
ligands as well as catalyzing covalent bond formation that
captures the threaded structure.48 New strategies for preparing
rotaxanes have emerged recently (Scheme 3). In a threading-
2. SYNTHESIS OF ROTAXANES BASED ON VARIOUS

MACROCYCLES
In this section, we focus on rotaxanes formed by templatedirected synthetic methodologies.51 Five types of typical
mechanisms (Scheme 2) for the construction of rotaxanes
can be identied. Scheme 2a demonstrates the capping method,
in which the macrocycle rst encircles the thread to form a socalled pseudorotaxane and a [2]rotaxane is then formed by end-
followed-by-shrinking strategy,56,57 the free space within the

macrocycle shrinks through coordination after the threading
process, while in a threading-followed-by-swelling strategy,58
the terminal group enlarges after the threading process.
Pseudorotaxanes and rotaxanes can be classied according to
dierent standards. On the basis of the dierence in the main
driving forces for the threading process, supramolecular
interactions that induce the formation of pseudorotaxanes
Scheme 3. New Strategies for the Construction of Rotaxanes
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Figure 3. Macrocycles used in the synthesis of rotaxanes.
the early plentiful work, crown ethers have become very

popular in cation complexation chemistry, and have been
utilized to prepare pseudorotaxanes and rotaxanes.
2.1.1. Bis(m-phenylene)-32-crown-10 and Crown
Ethers with Larger Sizes. Bis(m-phenylene)-32-crown-10
(BMP32C10) and crown ethers with larger sizes were initially
tried to construct hostguest complexes. In 1987, Stoddart and
co-workers demonstrated that BMP32C10 binds paraquat and
diquat dications in acetone.71 The main driving forces were
attributed to donoracceptor stacking interactions
between the complementary aromatic units, as well as C
HO hydrogen bonding and N+O electrostatic interactions.
On the basis of this hostguest recognition, [2]rotaxanes
containing the BMP32C10 or bis(p-phenylene)-34-crown-10
(BPP34C10) macrocycle and the axle with one or more 4,4bipyridinium units were constructed through both the clipping
and the slipping methods.7274 To investigate the stopper
eects on the properties of rotaxanes, bulky dendrimers were
covalently attached to rotaxane cores to aord [2]-, [3]-, and
[4]rotaxanes incorporating BPP34C10 wheels as the ring
components.75
Besides 4,4-bipyridinium units, other electron-decient
aromatic derivatives like pyromellitic diimide (PmI) and
naphtho-diimide (NpI) also complex with larger crown ethers
containing aromatic rings through similar interactions to
construct MIMs. For example, dinaphtho-38-crown-10
(DNP38C10) was used to form a [2]rotaxane with a dumbbell
component containing both PmI and NpI units.76 Very
recently, dimethyldiazaperopyrenium dication (MP2+), a electron-poor organic molecule, was used as a guest molecule
to construct [2]rotaxanes and a [3]rotaxane with DNP38C10
and BPP34C10 to investigate its chameleonic homo- and
and rotaxanes can be divided into hydrogen bonding,

hydrophilichydrophobic interaction, metalligand coordination, stacking, and charge transfer, among others.9,5961
On the basis of the dierence in reaction type, the widely
utilized chemical reactions for rotaxane synthesis are
Williamson ether synthesis, amide and ester bond formation
reactions, Glaser and Eglinton couplings, imine-bond formation, metalligand coordination, the Menschutkin alkylation
of pyridines with alkyl halides, the copper(I)-catalyzed azide
alkyne cycloaddition (the CuAAC click reaction), and other
types.6269 Here, we will discuss the construction of rotaxanes
according to the types of wheel-like macrocyclic molecules,
such as crown ethers, cyclodextrins, cucurbiturils, calixarenes,
pillararenes, tetracationic cyclophanes, amide-based macrocycles, and metalligand-based macrocycles (Figure 3). In
this way, we will have a clear picture about which type of
macrocycle is appropriate to prepare rotaxanes, and also the
dierences and advantages among various wheel-like molecules
are clearly known. Because of the complicated structures and
unique features, oligorotaxanes and their formations will be
summarized in this subsection independently. Besides, some
special phenomena in the synthetic process such as isomeric
properties will also be discussed. As a special supramolecular
system, rotaxane-related hostguest complexes based on
molecular tweezers and clips will also be discussed in this
section.
2.1. Crown Ethers
Crown ethers, which were rst discovered by Charles Pedersen

in 196770 and subsequently rapidly developed on a large scale,
consist simply of a cyclic array of ether oxygen atoms linked by
organic spacers, typically CH2CH2 groups (Figure 3). Since
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Scheme 4. Formation of [2]- and [3]Rotaxanes Based on the DNP38C10/MP2+ and BPP34C10/MP2+ Molecular Recognition
Motifs
heterophilic recognition nature (Scheme 4).77 Complexation of

MP2+ derivative 1 with DNP38C10 rst forms a pseudorotaxane with a binding constant of 1.05 104 M1 in acetonitrile.
After copper-catalyzed [3+2] cycloaddition to stopper the
complex with 2, [2]rotaxane 32PF6 was aorded in 22%. When
BPP34C10 was used as the wheel instead, [2]rotaxane 42PF6
and [3]rotaxane 52PF6 were obtained in yields of 14% and 4%,
respectively. The [3]rotaxane 52PF6 with two BPP34C10 rings
onto a single MP2+ recognition site oers a rare example of a
rotaxane in which two donor rings share one acceptor unit in
the dumbbell.
T h e la r g e r m a cr o cy c l e d i n a p h t h o - 5 0 - cr o w n - 1 4
(DNP50C14), containing two 1,5-dioxynaphthalene (DNP)
units similar to DNP38C10, clips two cyclobis(paraquat-pphenylene) rings (CBPQT4+) to form a donoracceptor
[3]catenane 68+ with a -electron-decient pocket (Scheme
5).78 Such [3]catenane acted as a host and formed a 1:1
complex with the guest 1,5-bis[2-(2-(2-hydroxyethoxy)ethoxy)ethoxy]naphthalene (BHEEEN) 7 to aord a [2]pseudorota[3]catenane 88+. However, the binding anity of
this [2]pseudorotaxane-type complex is very weak in CH3CN,
with a binding constant of 33 12 M1 measured by UV/vis
spectroscopic titrations. It was shown by X-ray crystallographic
analysis of the superstructure that the polyether loops in 88+
prevented the tri(ethylene glycol) chains in BHEEEN from
garnering any signicant [CHO] interactions with 88+.

Exchanging eight Cl anions for eight PF6 counterions
decreased the solubility in water. By contrast, the very stable
1:1 complex could be obtained in water based on hydrophobic
interactions.
2.1.2. Dibenzo-24-crown-8. Besides the large crown
ethers, dibenzo-24-crown-8 (DB24C8) is usually considered
as a wheel to form pseudorotaxanes with secondary ammonium
cations. Early studies found that secondary dialkylammonium
salts bound DB24C8 strongly and resided within the
macrocyclic cavity.79 The main driving forces are N+HO
and CHO hydrogen bonds between the hydrogen atoms of
the NH2+ and NCH2+ groups of the guest and the polyether
oxygen atoms of the host. The association constant (Ka) of the
complex based on DB24C8 and dibenzylammonium hexauorophosphate was determined in a range of solvents (from
DMSO of 0 Ml to CDCl3 of 27 000 Ml) by a single-point
1
H NMR spectroscopic determination performed at 298 K.80
One example of nding appropriate guests for BPP34C10 and
DB24C8 in one-pot systems was reported by Huang and coworkers.81 By taking advantage of the strong complexations
between DB24C8 and the dibenzylammonium moiety and
between BPP34C10 and the paraquat unit, two AB-type
heteroditopic monomers 9 and 10 were designed (Scheme 6).
Such self-sorting organization of the two monomers indicated
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Scheme 5. Chemical Structure and X-ray Crystal Structure of the [2]Pseudorota[3]catenane 88+ Based on DNP50C14a
Reproduced with permission from ref 78. Copyright 2012 American Chemical Society.
Scheme 6. Self-Sorting Organization of Heteroditopic Monomers 9 and 10a
based on the DB24C8/dibenzylammonium cation recognition

was prepared (Scheme 7).92,93 In this synthesis process,
cyclophane 12 was reacted with DCC-derived [2]pseudorotaxane 13 (DCC = N,N-dicyclohexylcarbodiimide)
to form [2]rotaxane 14. Subsequent modication of the
DB24C8 component introduced arginines to the ring through
DCC coupling with a catalytic amount of HOBt. Such a
cyclophane-modied [2]rotaxane is required for the intracellular delivery of a series of uoresceinated peptides.
Besides secondary ammonium cations, paraquat derivatives
have been considered as guests of DB24C8 and seemed not to
be good candidates for recognition of the host.96 As compared
to paraquat, the N+N+ distance in 1,2-bis(pyridinium)ethane
(BPE) decreases from 7.00 to 3.75 . This dierence leads to
dierent binding properties of the two compounds.97 Loeb and
co-workers reported that BPE dications thread DB24C8 wheellike compounds stabilized by N+O electrostatic interactions,
CHO hydrogen bonds, and -stacking interactions between
the electron-rich catechol rings of the crown ether and the
electron-poor aromatic rings of BPE.98 On the basis of this
recognition motif, [2]rotaxanes containing BPE axles and 24-
the dierent binding abilities of DB24C8 and BPP34C10. It led

to the alternating arrangement of the two monomers, which
further self-organized into a linear supramolecular alternating
copolymer 11.
The recognition motif between dialkylammonium cations
and 24-membered crown ethers has provided a very good
platform for fabrication of rotaxanes. The wheels include
DB24C8 or dipyrido-24-crown-8 (DP24C8), and the axles
contain one or more dialkylammonium sites. Through the
capping strategy, bulky stoppers can be introduced into
pseudorotaxanes by the triazole formation protocol,82 thiol
ene click reaction,83 urea formation,84 triphenylphosphonium
formation,85 Wittig reactions,86 alkene formation via ruthenium-catalyzed metathesis,87 and Sonogashira coupling.88
Recent studies on such rotaxane formation were focused on
modifying functionalized moieties such as fullerenes, calix[4]arenes, porphyrins, other cyclophanes, and uorescent moieties
in the terminal groups of the axles or the branches of the ring
components of rotaxanes to achieve some special functions.8995 For example, with the purpose of delivery of
uoresceinated peptides across cell membranes, [2]rotaxane 16
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Scheme 7. Formation of Cyclophane-Modied DB24C8-Based [2]Rotaxane 165TFA
Figure 4. Formation of [2]rotaxanes based on the DB24C8/BPE recognition motif.
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Scheme 8. Formation of [2]Rotaxanes [22-H][BF4] and 22 Based on the DB24C8/Benzimidazolium Molecular Recognition
Motif
crown-8 type wheels were constructed with either symmetrical

or nonsymmetrical conformations (Figure 4).99 Because both
the BPE axle and the crown ether wheel have dierent end
groups, the resulting [2]rotaxane 19 can exist in two distinct
coconformations.
To expand the guest classes, cations such as N-benzylic
anilinium100 and N-alkyl secondary anilinium moieties101 have
been used as guests for DB24C8-type wheels. Very recently,
Loeb and co-workers reported another new recognition
template between DB24C8 and a benzimidazolium axle with
extended aromatic substituents to form a [2]pseudorotaxane
and [2]rotaxanes (Scheme 8).102 The benzimidazolium salt
[20-H][BF 4 ] complexed with DB24C8 to form [2]pseudorotaxane [21-H][BF4], in which the wheel adopted a
C-shape conformation. The main interactions for the complexation contain NHO hydrogen bonding between benzimidazolium NH groups and DB24C8 ether oxygen atoms and
N+O iondipole interactions as well as -stacking of the
benzimidazolium rings with the catechol rings of DB24C8.
Besides, there are four additional CHO interactions
between DB24C8 oxygen atoms and aromatic hydrogens,
suggesting the signicant role of the addition of the aromatic
substituents to the increase in the association strength between
the axle and wheel. [2]Rotaxane [22-H][BF4] was prepared
through condensation of a diamine with an aldehyde followed
by catalytic oxidation. Deprotonation of [22-H][BF4] produced
[2]rotaxane 22. Without iondipole interactions and signicant
driving force for -stacking, the DB24C8 mocrocycle in
[2]rotaxane 22 adopts a more open conformation and shows
a rapid shuttling movement between the two equivalent
recognition sites on the ends of the rigid axle.
Besides the introduction of functional groups on rotaxanes,
the interest in DB24C8-based rotaxanes also comes from the
development of synthetic methods and improvement of the
reaction conditions. Hirose and co-workers reported the
synthesis of a 24C8-based [2]rotaxane via aminolysis of
prerotaxane compounds (Scheme 9).103 The intermediate
compound 24 was obtained through esterication of a phenolic
crown ether with an acid chloride. Subsequent aminolysis with
Scheme 9. Synthesis of [2]Rotaxane 25 via Aminolysis of

Prerotaxane 24 and Chemical Structure of 26
an amine having a bulky group in C6H6 gave [2]rotaxane 25 in

82% yield. This reaction also had a high [2]rotaxane selectivity
without the possible compound 26 (Scheme 9), which might
result from the participation of the crown ether ring for the
acceleration of aminolysis. It was conrmed that the
substituents on the axle unit of the prerotaxane exerted a
signicant eect on the rotaxane selectivity.
To improve the reaction conditions, a solid-state reaction
was tried to prepare rotaxanes and proved to be successful.104
By adopting a capping method and choosing a suitable
stoppering reaction, DB24C8-based rotaxanes were obtained
via an ecient solvent-free approach. Chiu and co-workers
reported a solid-state ball-milling reaction to prepare both [2]and [4]rotaxanes in high yields. As described in Scheme 10,
concentrating a solution of DB24C8 and trisammonium salt
27-H33PF6 in CH3CN aorded a solid. Upon mixing with
diamine 28, the corresponding [4]rotaxane 29-H33PF6 was
isolated in 78% yield. This approach was convenient, waste-free,
and complementary to the rotaxane preparation methods in
solution.
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Scheme 10. Solid-State Synthesis of [4]Rotaxane 29-H33PF6a
Reproduced with permission from ref 104. Copyright 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
2.1.3. Benzo-21-crown-7. Huang and co-workers demonstrated that secondary dialkylammonium salts thread the cavity
of benzo-21-crown-7 (B21C7) (Scheme 11).105 The related
binding constants (5271062 M1 in acetone) were higher
than the corresponding values (135261 M1 in acetone) of
the analogous complexes with the traditionally used host
DB24C8. On the basis of this B21C7/secondary dialkylammonium salt recognition motif, [2]rotaxane 32PF6 with two small
phenyl groups as the stoppers was successfully prepared in 74%

yield. It was conrmed by X-ray crystallographic analysis that all
four N-methylene hydrogens and two N-H hydrogens of the
dumbbell-shaped component 30PF6 were involved in nine
hydrogen bonds (Scheme 11) with the oxygen atoms of
B21C7, indicating the good size t between the host and guest.
Furthermore, pyrido-21-crown-7 (P21C7) was synthesized
and shown to form [2]pseudorotaxanes spontaneously with
secondary dialkylammonium ions.106 The association strengths
of these complexes are stronger than those of their B21C7
counterparts and much stronger than those of their DB24C8
counterparts. With the similar 21-crown-7 (21C7) macrocycle,
a smaller [2]rotaxane was obtained in high yield (81%) by ballmilling of a [2]pseudorotaxane formed from dipropargylammonium tetrauoroborate and 21C7 on SiO2 with 1,2,4,5tetrazine.107 Besides, a series of [2]rotaxanes were prepared
very recently by encircling 20-, 21-, and 22-crown ethers onto
the dibenzylammonium dumbbell.108 On the basis of the crown
ether/dibenzylammonium hostguest recognition motif and
using triuoromethyl as stopper, the smallest [2]rotaxane
reported so far containing a 20-member-crown ether macrocycle was synthesized.109
As described above, a phenyl group can not thread the cavity
of B21C7, but it can easily enter the cavity of DB24C8.80 On
the basis of this literature knowledge, Schalley and co-workers
designed and synthesized a four-component self-sorting system
consisting of B21C7, DB24C8, 30PF6, and 33PF6 (Scheme
12).110 It was conrmed that B21C7 forms [2]pseudorotaxane
35PF6 with guest 30PF6, because a phenyl group could not
pass through the cavity of B21C7 under the experimental
Scheme 11. Synthetic Route to and X-ray Crystal Structure

of [2]Rotaxane 32PF6 Containing B21C7a
a
Hydrogen-bond parameters: HO distances (), C(N)HO
angles (deg) A, 2.48, 152; B, 2.48, 122; C, 2.43, 150; D, 2.56, 144;
E, 2.72, 144; F, 2.50, 129; G, 2.04, 154; H, 2.11, 140; I, 2.33, 139.
Reproduced with permission from ref 105. Copyright 2007 American
Chemical Society.
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Scheme 12. A Four-Component Self-Sorting System Constructed from an Equimolar Mixture of B21C7, DB24C8, 30PF6, and
33PF6
Scheme 13. Formation of Sequence-Specic Hetero[3]rotaxane 382PF6
workers designed and prepared a series of cryptands based on

bis(m-phenylene)-32-crown-10 (BMP32C10) (Figure 5,
39),117125 which was a type of bicyclic crown ethers
containing two 1,3,5-phenylene units linked by three bridges.
They not only oer much better binding anities than the
corresponding simple crown ethers, but also can be used to
form pseudorotaxanes and rotaxanes with various small organic
guests such as paraquat, bisparaquat, diquat, diazapyrenium,
monopyridinium, bispyridium, trispyridinium, and imidazolium
salts (Figure 5).117125
The signicant improvement in the complexation of crown
ether-based cryptands is a result of the combination of the
preorganization of the cryptand hosts and the introduction of
additional and optimized binding sites. For example, the pyridyl
ester cryptand 39b, which has a pyridyl nitrogen atom located
at a site occupied by either a water molecule or a PF6 anion in
analogous complexes, exhibited the highest association constant
Ka = 5.0 106 M1 with paraquat in acetone, which is 9000
times higher than the corresponding simple crown ether
system.126 Furthermore, a supramolecular cryptand containing
BMP32C10 diol, with the assistance of a triuoroacetate anion,
displayed a 6.8-fold increase in Ka.127 The following studies
showed that a pseudorotaxane formed from a supramolecular
cryptand that resulted from the interaction of the CH2OH
moieties with a water molecule, increasing the number of N
HO hydrogen bonds between the host and guest.128130
Although usually the BMP32C10-based cryptand/paraquat
complexes show 1:1 stoichiometry in solution, the gaseous
state, and the solid state based on 1H NMR, mass spectral
characterization, and X-ray analysis, complexes of 2:1
conditions, while DB24C8 thermodynamically preferred 33PF6

over 30PF6, which resulted in the formation of [2]pseudorotaxane 34PF6. On the basis of the above self-sorting
pattern, the sequence-specic hetero[3]pseudorotaxane 37
2PF6 was expected to prevail in an equimolar solution of
B21C7, DB24C8, and 362PF6 in noncompetitive solvents.
Hetero[3]rotaxane 382PF6 (Scheme 13) then was synthesized
by treating the hetero[3]pseudorotaxane 372PF6 with benzoic
anhydride in the presence of tributyl phosphine as the catalyst
in 70% yield. Subsequently, deriving from the above simple
four-component self-sorting system, six ditopic key compounds
were used to self-assemble multiply threaded complexes with
high positional control.111,112 ESI mass spectrometry and, in
particular, tandem mass spectrometric experiments were used
to unravel the details of the complicated structures of these
multiply threaded complexes.
Considering the easy availability of B21C7 derivatives, their
ecient binding ability for secondary dialkylammonium salts,
and their smaller size making it easier to nd stoppers for
preparation of rotaxanes, various pseudorotaxanes and rotaxanes based on B21C7 were successfully prepared and used in
the construction of supramolecular polymers with functions of
environmental responsibility, gelation, and logic gates,113,114
which will be described in section 5.2.
2.1.4. Crown Ether-Based Cryptands. To construct
rotaxanes more eectively, the improvement of association
constants is important. For this purpose, crown ether-based
cryptands have been explored.115 After the rst dibenzo-30crown-10 (DB30C10)-based cryptand was reported by
Stoddart and co-workers in 1985,116 Gibson, Huang, and co7407
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Figure 5. Chemical structures of BMP32C10-based cryptands and their guests.
Scheme 14. Synthesis of [2]Rotaxane 494PF6 and [3]Rotaxane 516PF6 Based on the Cryptand/Paraquat Recognition Motif
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Scheme 15. Schematic Illustration of the Formation of Linear Supramolecular Polymers by Self-Assembly of AA Monomers 52
and 53, Respectively, with BB Monomer 54a
Scheme 16. Synthesis of Cryptand-Based [2]Rotaxanes 582PF6 and 603PF6
cryptand 39a and paraquat in the solid state.131 On the other

hand, bisparaquat guest 47 was also used in the preparation of a
stoichiometry do exist, which was evidenced by the crystal

structure of a [3]pseudorotaxane-like complex based on
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[3]pseudorotaxane with cryptand 39a, and the complexation

appeared to be cooperative.132 Because of the strong
BMP32C10-based cryptand/paraquat association, Huang and
co-workers prepared a series of MIMs.133135 For example,
[2]rotaxane 494PF6133 and [3]rotaxane 516PF6134 (Scheme
14) were obtained with high yields (92% and 86%, respectively)
by the capping strategy.
Still on the basis of the BMP32C10-based cryptand/paraquat
recognition motif, Gibson and co-workers designed and
synthesized two biscryptand hosts 52 and 53, one bearing a
terephthalic linkage and the other with a 1,10-ferrocenedicarboxylic linkage, which can be viewed as AA monomers (Scheme
15).136 A bisparaquat BB monomer 54 then self-assembled with
these biscryptands, respectively, to produce AA-BB-type linear
supramolecular polymers. These supramolecular polymers with
relatively high molecular weights have well-dened pseudorotaxane structures, which provide a promising route to form
rotaxane units by attachment of bulky stoppers to the ends of
difunctional bisparaquat derivatives.
Besides BMP32C10 and DB30C10, crown ether moieties
such as bis(m-phenylene)-26-crown-8 (BMP26C8)137139 and
DB24C8140 were also incorporated into cryptands and
supramolecular cryptands to form pseudorotaxanes and
rotaxanes. For example, Liu and co-workers used pyridine
cation derivatives to template the [2+3] clipping reaction
between simple aldehyde 55 and amine precursor 56 through
6-fold imine bond formation (Scheme 16). When the template
was dumbbell-shaped paraquat-containing 57, [2]rotaxane 58
was obtained;137 if the tricationic species 59 was used as the
template, [2]rotaxane 60 formed.138 The driving forces for the
formation of such [2]rotaxanes included interactions, and
multiple [CHO] and [CHN] hydrogen-bonding
interactions.
Triptycene-derived cylindrical macrotricyclic polyethers are
cryptand analogues, which were developed by Chen and coworkers.141148 Dierent from those macromonocycles and
macrobicycles, the macrotricyclic hosts 61ac contain one
central cavity and two lateral circular cavities, which incorporate
a rigid triptycene unit and link through four bridges (Figure
6).143 These specic topological features enhance their
complexation abilities toward various substrates.149 It was
found that host 61b forms stable 1:1 or 1:2 complexes in
dierent complexation modes with dierent functional paraquat
derivatives in solution and in the solid state, in which the two
alkyl groups of the paraquat unit threaded the two lateral crown
ether cavities of the host. Especially, the association constant
for the 1:1 complexes reached 4.0 105 M1 in a 1:1 CDCl3/
CD3CN solution. Besides paraquat derivatives, the cylindrical
macrotricyclic host 61b also self-assembled with two
dibenzylammonium salts to form a stable 1:2 [3]pseudorotaxane in solution and in the solid state, in which
multiple hydrogen-bonding and stacking interactions
between the host and guest played an important role.
Furthermore, a series of dendritic pseudorotaxanes was
constructed, and the structures were studied in detail.150
When one triptycene unit in 61b was replaced by an
anthracene unit, host 62 was obtained and it showed dierent
binding properties (Figure 6). An interesting sandwich
structure with the guest out of the cavity and positioned in
the middle of two of the hosts in the solid state was made on
the basis of the additional stacking interactions between
the anthracene unit and the guest molecules.151 Besides
triptycene, pentiptycene derived bis(crown ether)s were also
Figure 6. Chemical structures of triptycene-derived crown ether hosts

and X-ray structures of their related pseudorotaxanes. Reproduced
with permission from refs 143 and 151. Copyright 2006 and 2007
American Chemical Society.
designed and synthesized, which showed good binding ability

with tetracationic cyclobis(paraquat-p-phenylene).146,147
By using the capping method, potassium-ion-templated
complexes containing host 61b and axle components with
anthraquinone units were synthesized in yields of 7881%
(Scheme 17).152 Such complexes were also obtained by the
slippage method. Because the potassium ions acted not only as
templates during the stoppering reactions but also as
nonslipping chocks to shrink the inner diameter of the wheel
cavity, the deslipping behaviors of the complexes with dierent
triazole stoppers by peeling o the potassium ions with 18crown-6 were further investigated. The results showed that
complexes 64a and 64b could be destroyed, but under the same
conditions the dumbbell and ring components of complex 65
remained interlocked. On the other hand, derived from the
complexation between host 61b and dibenzylammonium salts,
a [3]rotaxane and hence a linear main-chain poly[3]rotaxane
were constructed by the ecient Cu+-catalyzed Huisgen 1,3dipolar cycloaddition.153
2.2. Cyclodextrins
Cyclodextrins (CDs) are a series of cyclic oligosaccharides

normally consisting of six (-CD), seven (-CD), or eight (CD) 14 -linked D-(+)-glucopyranose units.154187 Several
other CDs are known including -cyclodextrin and -cyclodextrin (9 and 10 units, respectively). They are distinguished by
the dierent ring sizes of homologous series (Figure 7). With a
lot of hydroxyl groups, CDs are water-soluble and biocompatible. Their truncated funnel-shaped cavity endows them with
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Scheme 17. Formation of Threaded Complexes 64ac and 65 Based on Triptycene-Derived Cylindrical Host 61ba
formation of CD-based rotaxanes.155158 In 1981, Ogino and

co-workers reported the synthesis of a CD-based [2]rotaxane. 1 5 5 By coupling Co I I I complexes to [2]pseudorotaxanes consisting of - or -CD threaded by 1,10diaminodecane in DMSO, [2]rotaxanes were obtained in yields
of 19% and 7%, respectively. Later, another two transition metal
complexes RuIII and FeII units were adopted as stoppers to
prepare rotaxanes in high yields.156,157 Ionic subunits between
tetraphenylboron and ammounium salts represent another type
of stoppers for the construction of CD-containing rotaxanes in
aqueous solution.159,160 To enhance the stability of the
threaded structures, covalent bonds are used to attach bulky
units. In this regard, Kaifer and co-workers did pioneering work
in 1991 through the snapping method.53 The ferrocene subunit
was adopted as one stopper to prevent -CD from dethreading
and a carboxylic acid group attached at the other end of the
chain to easily snap the [2]pseudorotaxane via standard
amidation procedures. On the other hand, an aromatic
nucleophilic substitution (SNAr) reaction between 2,4,6trinitrobenzenesulfonic acid sodium salt and diamino derivatives resulted in CN bond formation to construct -CD
rotaxanes with trinitrophenyl groups as stoppers.161,162 Other
ways to construct CD rotaxanes based on covalent bonds
involve aqueous Suzuki coupling reactions,163 reactions of
azobenzene diazonium salts with aqueous -naphthol derivatives,164 reactions of isothiocyanate compounds with amino
derivatives,165 and enzyme-catalyzed acylation.166
Satisfying the hydrophobic property and the appropriate
diameter size, many linear compounds can be used as axles for
the construction of CD-based rotaxanes, such as [R(CH2)nR]m+ (m = 02, R or R = pyrazine, bipyridine,
amino, or carboxylic groups),167171 and paraquat or reduced
paraquat derivatives.172 To change the optical properties or to
utilize photoisomerization, uorescent moieties including
stilbene and tolan units,163,173 the cyanine group,174 and the
tolidine diazonium salts175 have been encapsulated in the cavity
of CDs to form rotaxanes. It was reported by Anderson and coworkers that the large macrocycle -CD simultaneously binds
two -systems with one stilbene and one cyanine dye to form
[3]rotaxanes (Scheme 18).176 [2]Rotaxane -CD68 was rst
prepared via Suzuki coupling of iodoterphenylenedicarboxylic
acid 67 and stilbene diboronic acid 66 in the presence of -CD
in 17% yield. This [2]rotaxane was conrmed to have a
Figure 7. (a) Chemical structure of -CD, and (b) the cartoon

representations of -, -, -CD with minimum internal diameters
indicated.186
unique complexation ability in aqueous solution mainly through

hydrophobic interactions, and/or other interactions such as
hydrogen bonds. The excellent binding property makes them
good candidates as wheel-like components for the construction
of inclusion complexes.
The most common strategy to synthesize CD-based
rotaxanes is the capping approach by attaching stoppers to
both ends of a linear axis molecule. Several conditions are
required because the hydrophobic driving forces need an
aqueous medium or highly polar solvent. First, the bulky
substituents should be hydrophilic. Second, the pseudorotaxane-like structure should not be dissociated in aqueous media.
Third, the coupling reactions should be carried out under mild
conditions without high reaction temperatures and inert,
anhydrous demand. Initially, coordination reactions with
metal complexes as the stopper units were applied to the
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[3]rotaxane -CD(68)2 and hetero-[3]rotaxane -CD(68

70) were thus obtained in yields of 87% and 18%, respectively.
Specically, [3]rotaxane -CD(6870) was easier to synthesize than [2]rotaxane -CD70 (in 11% yield).
Recent studies found that other -conjugated compounds
containing anthracene,177 thiophene,178 tetrathiafulvalene
(TTF),179 and oligoresorcinol moieties180 also seem to be
good candidates for CD threading. For example, using Suzuki
coupling, two -CD-based [2]rotaxanes 73 and 74 containing
anthracene177 and bithiophene threads,178 respectively, have
been synthesized (Scheme 19). With the protection of -CD
rings, the uorescence quenching and chemical attack on the
anthracene moiety and the aggregation of dithiophene were
prevented eectively.
Bulky groups that act as stoppers for rotaxane formation play
a role as important as the axle units containing the interaction
sites. Harada and co-workers found that methyl-substituted
pyridyl groups kinetically control the threading of -CD onto
axle molecules.181,182 One methyl group at the 2-position of the
pyridinium part decreases the rate of complex formation as
compared to the case with no substitution on the pyridyl unit.
However, two methyl groups at the 3-,5-positions or the 2-,6positions of the pyridinium part prevent -CD from passing.
Takata and co-workers investigated size-complementary groups
to end-cap the -CD cavity (Scheme 20).183 It was found that
2-bromophenyl isocyanate but not phenyl- or 2-methylphenyl
isocyanate acted as an end-cap group to react with [3]pseudorotaxane 75 to produce [3]rotaxane 76 in a high yield of
73%, which was suciently stable at room temperature. After
heating at 100 C in DMSO, the threaded structure 76
dissociated and both [2]rotaxane 77 and dumbbell-shaped
molecule 78 formed. As the deslippage of 76 was stepwise and
the deslippage rate of 77 was slower than that of 76, the
[2]rotaxane 77 was isolated in 54% yield. Such a stepwise
deslippage process has been rarely observed in other
thermodynamic studies.
Selective functionalization of CD rings provides the related
rotaxanes with interesting physical properties, dierent
motions, and additional hostguest interactions.165,184,185 The
successful modication of CD-based rotaxanes with multivalent
carbohydrate groups was reported as a typical example (Scheme
Scheme 18. Synthesis of -CD-Based [3]Rotaxane CD(6870)
substantial cavity and then acted as a host to bind another

linear compound such as 66 or cyanine dye 69. Homo-
Scheme 19. Synthesis of CD-Based [2]Rotaxanes Containing Anthracene and Bithiophene Units
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Scheme 20. Synthesis of the Size-Complementary -CD-Based Rotaxanes
Scheme 21. Synthesis of the Carbohydrate Linked -CD-Based Rotaxanes
21).185 The preparation of such interlocked molecules involved

click chemistry. Capping 81 with N-propargyl lactosylamide
gave [2]rotaxane 83 in 54% yield, and assembling of double
molecules of 80 by bis-propargyl spacers 84 aorded
[3]rotaxane 85 in 24% yield. Here, saccharidic ligands were
introduced on rotaxanes both as biological recognition
elements and as capping groups. Their ability to inhibit the
binding of Arachis hypogaea agglutinin to asialofetuin was
assessed by enzyme linked lectin assays.
The inclusion complexes based on CDs have the ability to
change the properties of the linear components inside the ring,
such as their chemical stability, uorescence eciency, and
solubility. Because of the capability of CDs on associating
various guest molecules such as drugs, nucleic acids, proteins,
and other biological substrates, CD-based rotaxanes have been
successfully utilized in many biological elds such as
uorescence sensing, drug solubilization and delivery, controlled release, and so on.186 Furthermore, CDs are suitable
macrocycles for the formation of polyrotaxanes. Such supra-
molecular polymers represent a large family, which is not

included here.20,187
2.3. Cucurbiturils
Cucurbit[n]urils (CB[n]s), each of which consists of n

glycoluril units with a hydrophobic cavity and two identical
carbonyl-laced portals, are an important family of macrocyclic
compounds prepared from the acid-catalyzed condensation
reaction of glycoluril and formaldehyde (Figure 8).188 Similar
to CDs, the hydrophobic interior of CBs provides a potential
site for inclusion of hydrocarbon molecules. However, there
also exist unique features for CBs. For example, the polar
carbonyl groups at the portals allow them to bind ions and
molecules through chargedipole and hydrogen-bonding
interactions. All of these make CBs attractive building blocks
for the construction of interlocked molecules, in particular
rotaxanes and polyrotaxanes.189
2.3.1. Cucurbit[6]uril. The cavity of cucurbit[5]uril is too
small to be threaded by axle molecules. Cucurbit[6]uril
(CB[6]) is the smallest member of this family useful in the
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Figure 8. Structure and cartoon representation of CB[n].
contruction of pseudorotaxanes and rotaxanes. The initial

examples of CB[6]-based [2]rotaxanes were constructed using
a molecular bead and triazole or spermine as guest
molecules.190193 Spermine had high anity (Ka = 107
M1) toward CB[6], and its terminal amine groups are easily
stoppered by bulky substituents (Scheme 22).191 It was
revealed by the X-ray crystal structure of [2]rotaxane 88 that
a CB[6] molecule was located tightly at the middle of the string
by strong hydrogen bonding between the two inside
protonated amine hydrogen atoms and the oxygen atoms at
the CB[6] portals.
On the basis of the above-described hostguest complexation, a lot of functional interlocked systems incorporating
CB[6] were explored by Kim and co-workers and other groups.
For example pseudorotaxane-terminated dendrimers were
produced by attaching diaminobutane units at the terminals
of commercially available polypropylimine dendrimers, and
then threading of CB[6] onto the terminals (Figure 9).194 This
investigation endowed these novel dendrimers with a
mechanism for reversible encapsulation and release of guest
molecules, which may nd useful application in the eld of drug
delivery.
In accordance with the recent studies, CB[6] also binds 1,4bis(alkylaminomethyl)benzene195 and bispyridinium ethylene
derivatives.196 For example, the association constant for the 1:1
complexation between CB[6] and bispyridinium ethylene is
(2.1 0.2) 106 M1 in 0.05 M NaCl solution. A rotaxane
derived from this complex was prepared in 38% yield (Scheme
23).196 Furthermore, a shuttling process of the wheel was
observed in [2]rotaxane 91.
CB[6] also associates with polymers to form polypseudorotaxanes or polyrotaxanes.197 If CB[6]-based pseudorotaxanes
have two stoppers with coordination properties, they can
further coordinate with metal ions to construct large, rigid
coordination polymers, which will be discussed in detail in
section 5.4.198
2.3.2. Cucurbit[7]uril. With larger cavity and portal sizes,
cucurbit[7]uril (CB[7]) has higher association anity toward
Figure 9. Pseudorotaxane-terminated dendrimer. Reproduced with

permission from ref 194. Copyright 2001 Wiley-VCH GmbH & Co.
KGaA, Weinheim.
larger guest molecules such as 2,6-bis(4,5-dihydro-1H-imidazol2-yl)naphthalene, protonated adamantanamine, dimethyl paraquat dication, ferrocene derivatives, triphenylmethane dyes, and
bis(pyridinium)-1,4-xylylene derivatives, which can not be
encapsulated in the cavity of CB[6] (Figure 10).199204 For
example, the binding constants of CB[7] for protonated
adamantanamine in 50 mM NaO2CCD3-buered D2O (pD
4.74) and ferrocene derivatives in water are as high as 1012 M1.
As one example of application, the exceptionally stable CB[7]
ferrocene pair serves as a replacement of the strong avidin
biotin system205 to immobilize a protein on a solid surface
(Scheme 24).206 The allyloxyCB[7] was rst synthesized and
anchored on an alkanethiolate self-assembled monolayer on
gold. Ferrocenemethylammonium units then were attached to
glucose oxidase by EDC coupling. Thanks to strong association
between the CB[7] unit and the ferrocene moiety, the
immobilization of ferrocenylated proteins on the CB[7]anchored gold substrate was achieved and subsequently
monitored by surface plasmon resonance (SPR).
Recent research indicated that CB[7] recognized protonated
oligoaniline 92 with high binding anity (Ka > 2.2 106 M1
in dilute aqueous acetic acid (5.9 mM HOAc, pH 3.5)).207 It
was utilized to prepare [2]rotaxane 94 in 52% yield by
reductive amination with aldehyde stopper 93 (Scheme 25). If
the amount of stopper was increased, the yield of [2]rotaxane
94 could be raised to 85%. The radical cation of the threaded
Scheme 22. Synthesis of [2]Rotaxane 88 Based on the CB[6]/Spermine Recognition Motif
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Scheme 23. Formation of [2]Rotaxane 91 Based on Inclusion Complexation between CB[6] and a Bispyridinium Ethylene
Derivative
Scheme 25. Synthesis of CB[7]-Based [2]Rotaxane 94
Figure 10. Typical guest molecules for CB[7].
CB[8] can bind two dierent guest molecules inside its cavity,
including an electron-decient molecule and an electron-rich
molecule, to form a stable 1:1:1 ternary complex, derived from
the enhanced charge-transfer (CT) interactions between the
guest pair inside the hydrophobic cavity of CB[8] (Scheme
26).210,211
Scheme 24. Immobilization of a Protein on Gold Surface

Based on the Ferrocene/CB[7] Interactiona
Scheme 26. Formation of [3]Pseudorotaxanes Based on

CB[8]
The cylindrical cartoon represents CB[7]. Reproduced with

permission from ref 206. Copyright 2007 American Chemical Society.
oligoaniline in the rotaxane is thermodynamically and kinetically stabilized by the presence of CB[7]. This implies that
encapsulation of conjugated polymers in cucurbiturils can have
more than just a passive insulating eect and can dramatically
change the oxidation potential of the threaded -system.
2.3.3. Cucurbit[8]uril. Dierent from CB[6] and CB[7],
cucurbit[8]uril (CB[8]) exhibits remarkable hostguest
properties, including the encapsulation of two aromatic guest
molecules such as naphthalene derivatives inside the cavity to
form stable 1:2 hostguest complexes.208 This makes CB[8] an
excellent nanoreactor to improve chemical reactions such as
stereospecic [2+2] cycloadditions.209 More interestingly,
Pseudorotaxanes based on CB[8] provide useful platforms

for the design and synthesis of redox-driven molecular
machines such as molecular loop locks, development of
redox-controllable vesicles, and detection of biologically
important molecules.212214 For example, through hostguest
interactions, CB[8] macrocycles were connected by a rigid
linker containing an electron donor and an electron acceptor
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thus it is impossible to synthesize rotaxanes with calix[4]arene

as a wheel component. A pioneering calix[4]arene-containing
rotaxane was constructed by Vogtle and co-workers in 1998
(Figure 11),218 in which two calix[4]arene units were employed
as stoppers.219
Recently, the anion-templated synthesis of a [2]rotaxane with
a wheel containing a calix[4]arene unit was reported by Beer
and co-workers.220,221 The calix[4]arene precursor incorporated electron-rich hydroquinone groups to facilitate
stacking interactions with the electron-decient pyridinium axle
component. As a part of the wheel component and functionalized with terminal amine groups, compound 100 complexed
with the axle 101Cl and then underwent clipping condensation
with an appropriate bis-acyl chloride derivative to form the nal
rotaxane 102Cl in a yield of 11% (Scheme 29).221
Although calix[4]arene can not encircle an axle-like
component in its cavity, its tetraurea derivatives are successfully
used as the framework to fabricate more complicated
multimacrocyclic compounds, which are helpful for further
formation of 4-fold [2]rotaxanes 103 (Scheme 30).222224 The
preorganized heterodimers were rst held together by a
hydrogen-bonded belt between the urea groups to form socalled [2]pseudorotaxanes. Two types of [2]pseudorotaxanes
were converted into rotaxanes either by attachment of bulky
stoppers using the capping strategy via DielsAlder reactions
(103a),223 or by fourfold ring closing metathesis using the
clipping strategy (103b).224
2.4.2. Calix[5]arenes and Calix[6]arenes as Wheels. As
compared to calix[4]arenes, the slightly larger calix[5]arenes
are potential wheel candidates for pseudorotaxane or rotaxane
formation. The solid-state structure of a calix[5]arene/nbutylammonium endo-cavity complex225 revealed that the
nitrogen atom of the included guest molecule was surrounded
by the oxygen atoms of the host. This might imply that
calix[5]arenes were suciently exible to allow for the
inclusion of secondary alkylammonium cations. This hypothesis
was proved to be correct by the formation of a calix[5]arene/
di-n-alkylammonium salt-based [2]pseudorotaxane (Scheme
31).226 The kinetics of assembly and disassembly of these
interpenetrated supramolecules were controlled by the length
of alkyl groups on the axle, whereas the extent of their
formation and their thermodynamic stability depended
predominantly on the counterion of the axle.
unit on each end with a proper angle, to form a cyclic oligomer,

which was considered as a molecular necklace 3.7 nm in
diameter and 1.8 nm in thickness (Scheme 27).215 Such selfassembly of topologically intriguing supramolecules may aord
insight into the fabrication of nanoscale objects with welldened structures and functions.
Scheme 27. Formation of a Molecular Necklace Based on
CB[8] and Its Crystal Structurea

Chemical Society.
A good example of the use of a CB[8] rotaxane to bind

another guest has been described by Urbach et al.216 The axle
moiety contained a viologen core to guide host threading and
promote the selective binding of a second guest. After
molecular recognition, a water-soluble [2]pseudorotaxane was
formed and treated with a saturated aqueous solution of KPF6
to be transferred eciently into an organic solvent (Scheme
28). Using a click reaction, tetraphenylmethane stoppers were
capped to the inclusion complex, and [2]rotaxane 97 was
obtained in 25% yield. Hence, water-soluble [2]rotaxane 98 was
also synthesized, which bound the 2,6-dihydroxynaphthalene
guest more eciently.
2.4. Calixarenes
2.4.1. Calix[4]arenes as Linkers or Stoppers. Calix[n]arenes, which contain phenolic units bridged by methylene
groups at meta-positions, have been widely used in supramolecular chemistry as platforms for the synthesis of articial
receptors due to their tunable size, versatility of derivatization
(both at the wide and at the narrow rims), and availability.217
However, as compared to crown ethers and cyclodextrins, they
have received less attention as building blocks for the
construction of interlocked supermolecules. For the calix[4]arene, the cavity is too small to be threaded by a linear guest;
Scheme 28. Synthesis of CB[8]-Based [2]Rotaxanes
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Figure 11. Chemical structure of [2]rotaxane 99 with calix[4]arene stoppers.
Besides paraquat derivatives, calix[6]arene derivatives also

form pseudorotaxanes with other cationic compounds.230,231
For example, the diazapyrenium-based axle threads into the
cavity of triphenylureidocalix[6]arene in apolar solution.230
This self-assembled supramolecular species has three components, the wheel, the axle, and its counterions, that can mutually
interact. The stoichiometry of the resulting supramolecular
complex depends on the nature and concentration of the
counterions.
Recently, a head-to-tail bis-calix[6]arene having the structure
of an oriented nanotube that is about 2.6 nm long and 1.6 nm
wide was prepared and characterized (Scheme 33).232 This
molecule acts as a wheel-type host and forms a pseudorotaxane
with a paraquat derivative as the axle.
2.4.3. Heterocalix[n]arenes or Calix[n]heteroarenes.
Heterocalixarenes, in which the methylene linkages of
calixarenes between the aromatic units are replaced by
heteroatoms such as sulfur, oxygen, and nitrogen atoms,
represent a class of interesting host molecules for their peculiar
supramolecular receptor properties.233235 However, very few
of them have been used as wheel-like components to construct
MIMs, possibly due to the small cavities of the heterocalix[4]arenes or the exible conformations of larger heterocalixarenes.
A notable exception is the nding of Chen and co-workers
(Scheme 34), who investigated [2]pseudorotaxanes and
[2]rotaxanes based on triptycene-derived extended (hetero)calixarenes.236241 By introduction of the rigid triptycene
moiety and naphthyridine subunits, the new oxacalixarenes
113a and 113b showed not only large cavities but also xed
conformations in solution and the solid state. They both form
1:1 [2]pseudorotaxane-type complexes with paraquat derivatives containing dierent functional groups. Subsequently, a
pair of isomeric [2]rotaxanes were synthesized by the capping
method in yields of 56% and 25%, respectively. Compounds
113a and 113b represent the pioneering examples of
oxacalixarenes acting as wheels for rotaxanes.
Another novel example of a pseudorotaxane structure with an
azacalix[8]pyridine as the wheel encapsulating an acetylidetetrasilver aggregate into its cavity was reported by Wang, Zhao,
and co-workers (Scheme 35).242 Azacalixheteroaromatics,243,244
with nitrogen bridges adopting sp2 and/or sp3 electronic
congurations, possess a good coordination ability to bind
metal ions because of the strong electron-donating nature of
N(R) bridging moieties.245 When the polymeric silver acetylide
complex and silver triate were mixed with azacalix[8]pyridine
114 in CH3OH/CH2Cl2, a pseudorotaxane structure formed.
Scheme 29. Formation of [2]Rotaxane 102Cl with

Calix[4]arene as Part of the Wheel
The calix[6]arene platform possesses an annulus large

enough to allow a suciently bulky and enlongated guest to
thread the ring. Early in 2000, Arduini and co-workers reported
[2]pseudorotaxane- and [2]rotaxane-type threaded structures
with a triphenylureidocalix[6]arene derivative as the wheel and
paraquat derivatives as axles (Scheme 32).227 In this type of
[2]pseudorotaxanes, it was found that the counteranions of the
paraquat species played an important role in the formation of
the complexes.228 The use of either hexauorophosphate or
tosylate salts for the dicationic threading species inuenced the
thermodynamic stability of the pseudorotaxanes and aected
markedly the threading/dethreading kinetics. However, for the
calix[6]arene/paraquat-based [2]rotaxanes, the strength of
intercomponent interactions could be inuenced by the length
of the axle as well as the nature of the solvent.229
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Scheme 30. Formation of 4-Fold [2]Rotaxanes 103a
Reproduced with permission from refs 223 and 224. Copyright 2005 American Chemical Society and 2006 Wiley-VCH Verlag GmbH & Co.
KGaA, Weinheim.
Scheme 31. Formation of a Calix[5]Arene/Di-n-alkylammonium Salt [2]Pseudorotaxanea
characteristics (Figure 12).256,257 First, they are highly symmetrical and rigid as compared to crown ethers and calixarenes,
and this aords their selective binding to guests. Second, they
are easier to functionalize with dierent substituents on the
benzene rings than cucurbiturils. The symmetrical pillar
architecture and electron-donating cavity of pillararenes are
particularly intriguing, and endow them with some special
hostguest properties258260 and self-assembling applications.261264
This structure represents a novel example of a cluster-centered

organometallic rotaxane among the reported organometallic
and hybrid organicinorganic rotaxanes.246,247
2.5. Pillararenes
Pillararenes are macrocyclic molecules made up of hydroquinone units linked by methylene bridges at para
positions.248255 Although the composition of pillararenes is
similar to that of calixarenes, they have dierent structural
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Scheme 32. Formation of Calix[6]arene-Based [2]Rotaxane 1082Bra
Scheme 33. Formation of a Pseudorotaxane Based on a Head-to-Tail Bis-calix[6]arene in the Solid Statea
2.5.1. Organic Solvent-Soluble Pillararenes. Pillar[5]arenes, which are composed of the electron-rich aromatic rings,
exhibit interesting hostguest properties with electron-accepting molecules such as paraquat and pyridinium derivatives,248,265,266 imidazolium cations,267 bis(imidazolium) dications,268 secondary ammoniums,269,270 and n-octyltrimethylammonium hexauorophosphate271,272 in organic media (Scheme
36). Li and co-workers investigated the binding modes and
complexation stoichiometries for two types of guests in detail
and found that pillar[5]arene formed 2:1 external hostguest
complexes with N,N-dialkyl-4,4-bipyridiniums, while it formed
1:1 pseudorotaxane-type inclusion complexes with polymethylene [(CH2)n] linked bis(pyridinium) derivatives
possessing appropriate chain lengths. On the basis of the
interactions between pillar[5]arene and paraquat units,
polyrotaxanes were successfully prepared with extremely high
yields by capping the chain ends with adamantyl moieties.273
Very recently, Huang and co-workers reported some
functional cavity-extended pillar[5]arenes containing electronrich naphthyl groups.274 It was indicated that by introduction of
additional binding sites for guests with electron-decient 4,4-
bipyridinium units, the binding anity could be enhanced

eciently. Besides, urea groups were also introduced into the
pillar[5]arene scaold to improve the binding ability of the
hostguest systems.275,276 A bis-urea-functionalized pillar[5]arene formed [2]pseudorotaxanes with linear alkyl dicarboxylates in the highly polar solvent DMSO. The hydrogenbonding interactions between the bis-urea hydrogens and
dicarboxylate oxygens played an important role in stabilizing
the novel [2]pseudorotaxanes alongside CH interactions.
Along with charge-transfer interactions occurring between
the electron-rich cavities of pillar[5]arenes and the encircled
electron-decient guest molecules, CH interactions
provide the main driving forces for the formation of
[2]pseudorotaxane complexes, as conrmed by Huang and
co-workers during the preparation of copillar[5]arenes (Figure
13).277 Interestingly, it was found that an n-hexane molecule
was symmetrically included in the cavities of homopillar[5]arene 116 and copillar[5]arene 117 to form [2]pseudorotaxanes, driven by multiple CH interactions.
Such hostguest chemistry of pillar[5]arene derivatives with
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Scheme 34. Formation of [2]Rotaxanes 113a2PF6 and 113b2PF6 Based on Triptycene-Derived Oxacalixarenesa
Scheme 35. Formation of Cluster-Centered Organometallic [2]Pseudorotaxane 115 Based on an Azacalix[8]pyridine Wheela
concentration. Moreover, rodlike bers were drawn from a high

concentration solution and observed by SEM.282
Mainly based on CH interactions, pillar[5]arene
derivatives also form stable interpenetrated complexes with
neutral bis(imidazole) guests.284 Stoddart and co-workers
found that uncharged aliphatic amines are also encapsulated
in the cavity of 1,4-dimethoxypillar[5]arene (DMP[5]). This
binding motif was exploited to prepare [2]rotaxane 119 via a
capping strategy using a condensation reaction between amine
and aldehyde (Scheme 37).285 Another example of pillar[5]arene to bind aliphatic amines was recently reported by Wang
and co-workers.286 In this way, bifunctional ureidopyrimidinones (UPy) were modied on the wheel, and pillar[5]arenebased supramolecular polypseudorotaxanes were constructed
by quadruple hydrogen-bonding interactions.
Although many guest molecules have been investigated for
pillar[5]arenes, the pseudorotaxanes and rotaxanes based on
pillar[6]arenes and pillar[7]arenes have rarely been explored.
Huang and co-workers investigated the complexation properties of 1,4-diisobutoxypillar[6]arene and 1,4-bis(n-propoxy)-
Figure 12. (a) Structure of per-hydroxylated pillararenes and (b)

cartoon representation of per-hydroxylated pillar[5]arene.
anes,278,279 [2]rotaxanes,280,281 and even polypseudorotaxanes.282,283 For example, an easily available copillararene
monomer 118 was used as a building block to construct linear
polypseudorotaxanes driven by quadruple CH interactions
(Figure 14).282 It was demonstrated by a combination of
various techniques that the formation of this polypseudorotaxane was highly dependent on the temperature and monomer
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Scheme 36. Structures of Pillar[5]arenes and Their Guest Moleculesa
chloroform, while the related pillar[5]arene and pillar[7]arene

derivatives showed no or weak complexation with the same
guest due to their smaller or bigger cavity sizes.256,257 The same
group also investigated the hostguest complexation of perhydroxylated pillar[6]arene with a series of bipyridinium salts in
solution.287 It was found that a [2]pseudorotaxane formed in
acetone with an association constant of 2.2 102 M1 between
the per-hydroxylated pillar[6]arene and paraquat. Moreover,
the complexation properties of pillar[n]arenes (n = 810) with
n-octyltrimethylammonium were reported by Hou and coworkers.288
2.5.2. Water-Soluble Pillararenes. To investigate the
binding property of pillararenes in aqueous media, watersoluble pillar[5]arenes have been prepared. In 2010, Ogoshi
and co-workers synthesized a water-soluble pillar[5]arene
containing 10 negative-charged carboxylate groups, which
bound cationic paraquat to form a [2]pseudorotaxane in
water.289 The binding behavior of the carboxylatopillar[5]arene
with substituted 1,4-bis(pyridinium)butane derivatives was also
investigated in aqueous phosphate buer solution, and in some
cases [2]pseudorotaxanes with large association constants
(>105 M1) formed.290 Subsequently, a water-soluble pillar[5]arene containing neutral amino groups was prepared by Hou
and co-workers; it encapsulated linear diacids under neutral,
alkaline, and acidic conditions and formed ion pair-stoppered
[2]rotaxanes.291 Recently, a cationic pillar[5]arene 120 bearing
trimethylammonium groups on both rims was synthesized by
Huang and co-workers.292 It was revealed to bind sodium 1octanesulfonate in aqueous media, forming a [2]pseudorataxane mainly driven by hydrophobic and electrostatic
interactions (Scheme 38).
Water-soluble pillar[6]arene (WP[6]) 121 containing 12
negative-charged carboxylate groups was rst prepared by
Huang and co-workers.258 WP[6] strongly encapsulated
organic pyridinium salt 122 in water, mainly driven by
hydrophobic and electrostatic interactions (Scheme 39a).
Without the host, the amphiphilic guest molecule 122 selfassembled into nanotubes in water. However, vesicles formed
upon addition of WP[6] to form a [2]pseoudorotaxane. The
reversible transformation between nanotubes and vesicles was
easily controlled by changing the solution pH (Scheme 39b).
Furthermore, by interacting with neutral guest 123, WP[6] was
Figure 13. Chemical structures of 116 and 117 and crystal structures
of 116n-C6H14 (a,c) and 117n-C6H14 (b,d). Hydrogens are
omitted for clarity; the atoms in macrocycles are red, oxygen atoms
are green, and n-hexane molecules are blue. The purple dotted lines
indicate CH interactions. Reproduced with permission from ref
277. Copyright 2010 American Chemical Society.
Figure 14. Structure of copillar[5]arene 118 (left) and two views of

the linear polypseudorotaxanes (right) in the solid state. Reproduced
with permission from ref 282. Copyright 2011 Wiley-VCH Verlag
GmbH & Co. KGaA, Weinheim.
pillar[6]arene with n-octyltrimethylammonium hexauorophosphate and found that both formed 1:1 complexes in
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Scheme 37. Formation of [2]Rotaxane 119 with DMP[5] as the Ring Componenta
Scheme 38. Formation of a [2]Pseudorotaxane from Water-Soluble Cationic Pillar[5]arene 120 and Sodium 1-Octanesulfonatea
cyclization of the ring to obtain the [2]rotaxane in 32% yield.

The low yield might result from various conformations of the
linear two-binding-site component in solution.
Hence, dierent molecular motifs with -electron-donating
nature have been chosen as part of the dumbbell components
of [2]rotaxanes, involving the p-xylyl unit, the 2,3,5trisubstituted indole unit, the tetrathiafulvalene (TTF) unit,
the benzidine unit, and the 1,5-dioxynaphthalene (DNP) unit
(Figure 15).295297 The structural diversity of the rotaxanes was
introduced by changing stoppers such as a benzylic alcohol, a
hydrophilic or hydrophobic stopper, or a dendritic mesogen.298300 By changing the interaction modes, the supramolecular architecture could accomplish the desired switching
behavior upon electrochemical or chemical stimulation.301
Because the CBPQT4+ ring is easily attacked by reducing
agents, bases, and nucleophiles, it is better to construct the
rings at the last stage. In most cases, the clipping method is
appropriate and eective for CBPQT4+-based rotaxane
formation. Recently, the capping approach was also exploited
to synthesize this type of bistable [2]rotaxane through click
reactions. As described in Scheme 41, a CBPQT4+-based TTF/
DNP rotaxane was synthesized by this method.302 The rst step
used in the pH-controlled reversible dispersion of multiwalled

carbon nanotubes (MWNTs) in water (Scheme 39c). These
new recognition motifs based on WP[6] have potential
applications in many elds, including supramolecular polymers,
nanoelectronics, sensors, and drug and gene delivery systems.
2.6. Tetracationic Cyclophanes
Broadly speaking, the term cyclophane means any macrocyclic molecule containing aromatic rings linked by aliphatic
bridges. There are a lot of cyclophanes and cages that have
been prepared up to now. One of the most famous cyclophanes
is cyclobis(paraquat-p-phenylene) (CBPQT4+), prepared by the
group of Stoddart.293 It is known as the blue box because of
the violet blue color of the radical cation formed upon oneelectron reduction of many paraquat derivatives. This electron-decient receptor binds a variety of -electron-rich
guests to construct MIMs. In 1991, a donor/acceptor
[2]rotaxane based on CBPQT4+ was prepared through the
clipping method (Scheme 40).294 At rst, the bispyridinium
dication reacted with 1,4-bis(bromomethyl)benzene to form a
bipyridinium unit, which had a strong ability to bind
hydroquinone sites on the dumbbell component. This
supramolecular complex served as a template for the nal
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Scheme 39. (a) Formation of [2]Pseudorotaxanes Based on Water-Soluble Pillar[6]arene 121 and Guest 122 or 123; (b)
Schematic Representations of the Reversible Transformations between 122-Based Nanotubes and 121122-Based Vesicles; and
(c) pH-Responsive Dispersion of MWNTs in Water in the Presence of 121123a
Scheme 40. Formation of a Donor/Acceptor [2]Rotaxane 1264PF6 Based on CBPQT4+
Recently, Stoddart and co-workers demonstrated that

paraquat radical cations form strong inclusion complexes with
the tetracationic cyclophane in its reduced diradical dicationic
state (CBPQT2(+)) as a consequence of radical-pairing
interactions.303 Subsequently, an unlikely [2]rotaxane 131
6PF6 composed only of electron-decient CBPQT4+ and
paraquat units with no complementary electron-rich components has been prepared by radical templation.304 As illustrated
in Scheme 42, CBPQT4+ initially had no interactions with
paraquat derivative 1302+. By using visible light to activate the
well-known [Ru(bpy)3]2+ reducing system (bpy = 2,2bipyridine), the bipyridinium units in compounds 1302+ and
CBPQT4+ were highly eciently reduced through photoinduced charge transfer. Thus, a [2]pseudorotaxane formed,
driven by radical dimer interactions. During the process,
triethanolamine, which was employed as the sacricial electron
donor, prevented back electron transfer from the bipyridinium
radical cation to the [Ru(bpy)3]3+ species. Synthesis of
[2]rotaxane 1316PF6 was achieved by the capping strategy
using a copper-free azidealkyne 1,3-dipolar cycloaddition with
a yield of 35%. This synthetic strategy provides a good method
for formation of MIMs that have little or no interaction
between host and guest components in their ground states.
Figure 15. Building units used for the dumbbell components of

[2]rotaxanes based on CBPQT4+.
was the formation of pseudorotaxane 1274PF6, wherein the electron-decient CBPQT4+ ring threaded onto a linear
molecule containing two -electron-rich recognition units.
The terminal azide groups of 1274PF6 underwent a Cu(I)catalyzed Huisgen 1,3-dipolar cycloaddition with the alkyne
compound 128, nally forming rotaxane 1294PF6 incorporating 1,2,3-triazole units in 60% yield. It provided a new eective
strategy for the preparation of switchable donor/acceptor
[2]rotaxanes and expanded their applications.
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Scheme 41. Synthesis of a CBPQT4+-Based [2]Rotaxane 1294PF6 Using Click Chemistry
Scheme 42. Radically Promoted Synthesis of a CBPQT4+-Based [2]Rotaxane 1316PF6a
The PF6 counterions were omitted for clarity.
1324+ was generated by Sessler and co-workers.305 With a facile

synthetic process in high yield, this macrocycle proved to bind
Along with the rapid development of the chemistry on the

CBPQT4+ macrocycle, a larger tetraimidazolium macrocycle
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Scheme 43. Schematic Representation of the Formation of Pseudorotaxanes Based on the Tetraimidazolium Macrocyclea
Scheme 44. Formation of Tetralactam Macrocycle-Based [2]Rotaxanes 136af
macrocycle and formed pseudorotaxanes. On the basis of the
aromatic anionic species eectively. Several pseudorotaxane and

rotaxane structures have been produced by using this molecular
receptor.306 For example, the complexation of this cyclophane
with 4,4-biphenyldicarboxylic acid and its anions was
investigated in detail (Scheme 43).307 It was revealed that the
diacid did not show any interaction with the ring. However,
both its monoanion and its dianion inserted into the
Job plot and NOESY NMR analyses, both complexes had a

binding stoichiometry of 2:3 (host:guest), with the excess guest
molecular anion sandwiched between two sets of individual
1:1 hostguest complexes.
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Scheme 45. High-Yielding Anionic Template Synthesis of Rotaxane 139 Based on Tetralactam Macrocycle 133
Scheme 46. Formation of Tetralactam Macrocycle 140 and Its [2]Rotaxane 142
2.7. Amide-Based Macrocycles
increase the template eect, the central part of the axle was
changed from a meta-phenylene to a para-phenylene unit, vemembered heterocyclic rings, sulfonyl groups, and so on.
Hence, a series of [2]rotaxanes (Scheme 44),311 as well as a
[3]rotaxane,312 were prepared in yields up to 41%.
In addition to the diamide guests described above, the
tetralactam macrocycles also exhibit strong anities toward
small inorganic anions as well as organic anions in nonpolar
solvents. For example, on the basis of the interaction between
the macrocycle and a phenoxide anion, a new anionic template
2.7.1. Tetralactam Macrocycles with Diarylmethane

Motif. In the early 1990s, Vogtle and Hunter independently
reported tetralactam macrocycles accompanied by the formation of catenanes.308,309 The isophthaloyl diamide groups
and the diarylmethane motifs on the macrocycle provide
multiple hydrogen-bonding sites and interaction sites for
recognition. Subsequently, on the basis of these interaction
sites, the early amide-based [2]rotaxane formed by the capping
strategy in 11% yield (Scheme 44).310 To improve the yield and
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hydrogen bonds formed between the amide groups in the

fumaramide thread and the isophthalamide ring without any
distortion; moreover, two DMF molecules were included as a
linker for the host and guest by hydrogen-bonding interactions
with the linear component and -stacking with both phenyl
stoppers and isophthaloyl rings. All of the above ndings
indicated that in a rigid linear backbone, multiple cooperative
binding sites were xed in an ideal spatial arrangement, which
allowed even poor hydrogen-bond acceptors such as esters
(Scheme 47, X = O) to be used to prepare such rotaxanes,
although with a relatively low yield. On the basis of this
powerful strategy, a variety of rotaxanes have been designed and
used to fabricate molecular machines.30
Besides various amide and ester compounds, neutral
squaraine units have also been employed as the threads to
construct benzylic amide macrocycle-containing [2]rotaxanes.22
Very recently, the hydrogen-bond acceptors in the thread were
extended to other ionic or mesomeric groups with signicant
hydrogen-bond basicity such as N+O, S+O, and P+
O.319321 For example, the bisnitrone thread 145 with the two
oxygen atoms at an opposite orientation similar to those of the
amide carbonyls in a dipeptide was utilized to synthesize
[2]rotaxanes 146ac (Scheme 48).319 When isophthaloyl
synthesis of rotaxanes was introduced with a surprisingly high

yield of 95% (Scheme 45).313 In the rst step, the phenolate
stopper inclined to form a supramolecular complex 137 with
macrocycle 133 via hydrogen bonding probably with the anion
positioned on top of the wheel. The intermediate phenolate
wheel complex then acted as a supramolecular nucleophile to
react with semiaxle 138 to furnish the [2]rotaxane 139. Further
investigation of this template motif by Schalley and co-workers
has revealed that recognition of the highly reactive phenoxide
anion by this tetralactam macrocycle inhibits its nucleophilic
reactivity. On the basis of this discovery, a [2]rotaxane was
generated by amine condensation reactions with sterically bulky
acyl chloride frameworks.314
2.7.2. Tetralactam Macrocycles with Benzylamide
Motif. The smaller tetralactam macrocycles incorporating
benzylamide units were subsequently developed by Leigh and
co-workers. Initially, the condensation of p-xylylenediamine
with isophthaloyl dichloride could only form the [2]catenane,
whereas macrocycle 140 was intractable from a mixture of other
precipitated cyclic oligomers and polymers.315 However, such
problems were overcome through satisfying hydrogen-bonding
requirements with other molecules (Scheme 46).316 A linear
molecule 141 acted as a hydrogen-bonding template for the
macrocycle, which led to the formation of [2]rotaxane 142 in
the yield of 28%. This is a nice example in that the [2]rotaxane
formation is a powerful means to alter the reaction product.
The isolated [2]rotaxane was disassembled via hydrolysis of the
ester groups to remove the large stoppers and release the
desired macrocycle. Furthermore, if a dipeptide axle incorporating glycylglycine was used as a template, which possessed
excellent complementary hydrogen-bonding sites to the
tetralactam macrocycle, a higher yield (62%) was obtained.317
To improve the synthesis of hydrogen-bonding-mediated
rotaxanes, preorganization of the hydrogen-bonding sites on
the axle by incorporating a rigid spacer was a successful
strategy, which showed a notable inuence on template
eciency.318 For example, with the fumaramide motif as a
good hydrogen-bond acceptor, a remarkable yield of 97% for
[2]rotaxane 144a was obtained (Scheme 47). The crystal
structure of this [2]rotaxane showed that four bifurcated
Scheme 48. Formation of Bisnitrone [2]Rotaxanes 146ac
Scheme 47. Templated Synthetic Route to [2]Rotaxanes 144

and X-ray Crystal Structure of [2]Rotaxane 144aa
dichloride was used, [2]rotaxane 146a formed in 70% yield.
Under analogous conditions, replacing isophthaloyl dichloride
with 2,6- or 3,5-pyridinedioyl dichloride aorded the
corresponding [2]rotaxanes 146b and 146c in 21% and 40%
yields, respectively. The solid-state structures of 146ac
showed that [2]rotaxanes 146b and 146c were driven by two
sets of bifurcated hydrogen bonds between the 1,3-diamide
groups of the macrocycle and the nitrone oxygen atoms, while
the isophthalamide macrocycle-based [2]rotaxane 146a adopted a solid-state structure dierent from the other two
rotaxanes. The amide-nitrone hydrogen bonds presented in
these systems are signicantly stronger than analogous amide
ester and even amideamide hydrogen-bonding interactions as
conrmed by dynamic 1H NMR experiments. This rotaxane
architecture protects the thread from chemical reduction with
an external reagent and increases the contribution of the C
N+(R)O canonical form relative to that of the CN+(R)
O form in comparison with simple nitrones.

Chemical Society.
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Scheme 49. Synthesis of Phosphinamide, Thiophosphinamide, and Selenophospinamide [2]Rotaxanes and the X-ray Crystal
Structure of One of Thema
After the investigation on the rotaxane formation based on

nitrone319 and sulfoxides groups,320 some phosphinic, thiophosphinic, selenophosphinic amides [(PX) NHR; X = O, S,
Se] and phosphine oxides were employed as hydrogen-bonding
templates in the rotaxane formation.321 When one amide group
of the classical glycylglycine template was replaced with a
phosphinamide unit (X = O, Y = NH, Z = C), a [2]rotaxane
was obtained in 60% yield (Scheme 49). The weaker
intercomponent hydrogen bonding was consistent with the
lower yields obtained in the synthesis of the PS and PSe
rotaxanes. In the cases of two such groups in the thread, the
bis(phosphinamide) rotaxane (X = O, Y = NH, Z = P) was
isolated in 18% yield, while no rotaxane could be detected in
the reactions involving the bis(thiophosphinamide) or bis(selenophosphinamide) threads (X = S or Se, Y = NH, Z = P).
X-ray crystallography of these rotaxanes showed the presence of
up to four intercomponent hydrogen bonds between the amide
groups of the macrocycle and phophosphinamide, thiophosphinamide, or selenophosphinamide groups on the thread.
Specially, there existed remarkable interactions for the
phosphine oxidephosphinamide rotaxane (X = O, Y1 = NH,
Y2 = O, Z = C) in the solid state, featuring no direct
intercomponent hydrogen bonds but rather a hydrogen-bond
network involving water molecules that bridge the H-bonding
groups of the macrocycle and thread through bifurcated
hydrogen bonds (Scheme 49). The incorporation of
phosphorus-based functional groups into rotaxanes may prove
useful for the development of molecular shuttles in which the
macrocycle can be used to hinder or expose ligating sites for
metal-based catalysts.
Recently, tetralactam macrocycle 140 was used to synthesize
polyrotaxanes by Gibson and co-workers.322 At rst, they
attempted to incorporate macrocycle 133 into a side-chain
polyrotaxane by reaction of tritylphenol with poly(vinybenzyl
chloride) but failed apparently due to steric hindrance. On the
basis of this macrocycle, they prepared three [2]rotaxanes.
However, by clipping tetralactam 140 onto a preformed
polyurethane in CH2Cl2, they got a single-phase polyrotaxane
with a signicantly lower glass transition temperature.
2.7.3. Other Lactam Macrocycles. Parallel to the work of
Vogtle and Leigh, Beer and co-workers have developed a
general anion template strategy based on lactam-containing
macrocycle 147 (Scheme 50).323,324 It was designed to
Scheme 50. (a) Schematic Representation for the Formation

of Anion-Template [2]Rotaxane; and (b) Chemical
Structure of Macrocycles 147 and 148 and
[2]Pseudorotaxane 149Xa

Chemical Society.
incorporate an isophthalamide anion binding unit so as to

saturate the halide anions coordination sphere of a pyridinium
ion-pair (Scheme 50). In addition, the introduction of
hydroquinone groups into the macrocyclic framework allows
stacking interactions with the pyridinium cation unit, and
the other polyether linkages are expected to aid interpenetration of the thread by providing additional hydrogenbonding interactions. These structural features make it possible
to eciently construct pseudorotaxanes with cationic thread
components including pyridinium nicotinamide, imidazolium,
benzimidazolium, and guanidinium functionalities.325,326 Besides, the isophthalyl unit in the macrocycle can be replaced by
another halide binding cleft such as the neutral rhenium(I)
bipyridyl-containing precursor (see macrocycle 148 in Scheme
50).219
[2]Rotaxanes based on anion templates have usually been
prepared by the clipping strategy via ring-closing metathesis
using Grubbs catalyst (Scheme 51). For example, an
orthogonal complex was formed after the macrocycle precursor
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Scheme 51. Formation of Chloride-Templated [2]Rotaxanes 152Cl and 152PF6a
Scheme 52. Anion-Templated Formation of [2]Rotaxane 155Br Based on an Iodotriazolium Axle
150 and ion-pair 151Cl were 1:1 mixed in solution.327 The

two vinyl groups in 150 were drawn together by anion
coordination. The [2]rotaxane 152Cl was subsequently
obtained in 47% yield through ring-closing metathesis reaction
in CH2Cl2 with the aid of Grubbs catalyst. It was noteworthy
that if the chloride anion was replaced by bromide, iodide, or
hexauorophosphate anion, no interlocked products could be
obtained. From removal of the chloride anion, the hexauorophosphate rotaxane 152PF6 formed, leaving a unique threedimensional anion-binding domain.
Halogen bonds forming between polarized halogen atoms
are considered to be formally noncovalent interactions to
integrate into the interlocked binding pockets. On the basis of
this hostguest recognition, Beer and co-workers reported the
use of halogen bonding to facilitate the chloride aniontemplated assembly of a 2-bromo-functionalized imidazoliumthreading pseudorotaxane.328 Subsequently, a [2]rotaxane was
synthesized by using such a halide anion-templated method.329
It was established that iodotriazolium halide salts were capable
of forming anion-templated interpenetrative assemblies. The

synthesis of the halogen-bonding [2]rotaxane 155Br then was
undertaken by reaction of bisvinyl-functionalized derivative 154
and iodotriazolium axle 153Br with Grubbs II catalyst in 15%
yield (Scheme 52). It was shown by the X-ray crystal structure
of [2]rotaxane 155Br that the bromide anion was coordinated
by both the triazolium iodine atom and the amide hydrogens.
The incorporation of the iodine atom into the cavity
signicantly enhanced the rotaxanes anion-recognition properties in comparison with the hydrogen-bonding analogue,
providing unusual selectivity for iodide.
Amide-based macrocycles also bind neutral urea compounds330 and secondary ammonium salts331 through intermolecular COHN hydrogen bonding. For example, Li
and co-workers prepared a type of amide-based two-layered
capsules by using dynamic covalent chemistry (DCC).331 The
binding ability of these compounds toward bisammonium
cations 157 and 158 was investigated. As described in Scheme
53, when mixing the host and guest molecules in 1:1 molar
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Scheme 53. Formation of Pseudorotaxanes 159a and 159b Based on Two-Layered Capsulea
Scheme 54. Formation of Metal-Templated [2]Rotaxane 163
design of new three-dimensional architectures for molecular

encapsulation or catalysis.
ratio, the ammonium guests inserted into the cavity of the

capsule and formed pseudorotaxane complexes, as conrmed
by 1H NMR spectra, 2D NOESY spectra, and ESI mass spectra.
The association constant (Ka) of the complex 159b was
determined to be 590 M1 in CDCl3 by uorescent titration.
These pseudorotaxanes with unique coconformations from the
capsule and aliphatic bisammonium ions bode well for the
2.8. Coordination-Based Macrocycles
All of the above examples involving templated syntheses of

rotaxanes are derived from hydrogen bonding, stacking,
hydrophobic, and/or charge-transfer interactions. In the
development of MIMs, metal templated synthesis is also a
very powerful strategy.332340 Macrocycle 160 containing 1,107430
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Scheme 55. Formation of Metal-Templated [3]Rotaxane 170 and [5]Rotaxane 171
Figure 16. Formation of Fe(II)-templated [3]rotaxane 175. Reproduced with permission from ref 341. Copyright 2008 American Chemical Society.
disubstituted phenanthroline ligands was designed by Gibson

and co-workers (Scheme 54).332 Metal ions such as copper ion
serve as a bridge to connect the macrocycle and a linear

molecule 161 also containing 1,10-disubstituted phenanthroline
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Scheme 56. CuAAC Active Template Synthesis of [2]Rotaxane 179 and [3]Rotaxane 180
unit together, resulting in the formation of a [2]pseudorotaxane

162. Further alkylation of the axle component with bulky
stoppers led to the formation of a copper ion coordinated
rotaxane.332,337 The template metal was selectively removed
from the complex by the ion-exchange with Amberlite resin to
aord the metal-free rotaxane 163 as the main product.
Unthreaded coupling product 164 was also obtained.
When the monochelating molecular thread was replaced by a
bis-chelating molecule, more complicated interlocked molecules could be designed and constructed.338,339 In an early
example, a metal-templated [3]rotaxane stoppered by porphyrin subunits was obtained by Sauvage and co-workers (Scheme
55).338 A compartmental tetracopper(I)-complexed [5]rotaxane also unexpectedly formed. At rst, macrocycle 160
formed a 1:1 complex with Cu(I), followed by the complex-
ation with 0.5 equiv of bisphenanthroline thread 165 to prepare

a binuclear [3]pseudorotaxane 166. This complex was
subsequently reacted with a mixture of (3,3-dihexyl-4,4dimethyl-2,2-dipyrryl)methane (167) and 3,5-di-tert-butylbenzaldehyde (168) in the presence of CF3CO2H. After
purication, (Cu)2-[3]rotaxane 170, (Cu)4-[5]rotaxane 171,
and a porphyrin derivative 169 were obtained in yields of 34%,
8%, and 32%, respectively. Furthermore, coordination chemistry of the (Cu)2-[3]rotaxane was investigated in detail.
In addition to the copper(I) metal center, a three bidentate
chelate-coordinated octahedral ruthenium(II) complex is also
an attractive template for preparing rotaxanes with larger
rings.340 Especially the [Ru(bpy)3]2+ family displays very
interesting electro- and photochemical properties in relation
to the construction of light-driven molecular machines.
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template reactions have been quickly developed, such as Cumediated alkyne homocoupling348 and Cu-catalyzed alkyne
alkyne heterocoupling.349 With these eective reactions, various
hetero- or homocoupled rotaxanes with excellent selectivity and
good isolated yields have been achieved. Furthermore,
palladium-catalyzed cross-coupling reactions were also successfully extended to synthesize rotaxanes, which greatly improved
the synthetic versatility of the active metal template method.
After failure using Pd(0)-catalyzed reactions, attention was
turned to Pd(II)-catalyzed homocoupling of alkynes, which was
proved to be eective for the formation of rotaxanes.350
Besides, Pd(II)-mediated Michael additions have also been
applied to prepare rotaxanes through this active metal template
method.351 The approach allows ready access to rotaxanes, in
which the intercomponent interactions can be designed to
enable the construction of molecular shuttles and other
molecular machine structures with the fastest possible
dynamics.352 The Pd(II) oxidative Heck cross-coupling has
recently been applied to the active metal template synthesis of
[2]rotaxanes, which shows mild, ecient, and substrate tolerant
properties (Scheme 57).353 The Pd(II) complex with the
The 2,9-diphenyl-1,10-phenanthroline (dpp) fragment, due

to its extended rigid backbone, has played a particularly
prominent role in the construction of MIMs based on metal
templates. To decrease the steric constraints and fabricate
complexes with more sophisticated topologies, more chelating
agents were explored for metal-templated synthesis of
rotaxanes. As described in Figure 16, the 8,8-diphenylsubstituted 3,3-biisoquinoline fragment (dpbiiq), with a
distance of 11 between the phenyl-rings attached to the
3,3-biisoquinoline backbone, oers a much more open
coordination site than the dpp ligand (whose distance between
the phenyl rings is only 7 ).341,342 This chelate was shown to
form octahedral complexes with Fe(II) or Ru(II) in high yields.
It was indicated that macrocycle 172 could be threaded by two
string-like compounds containing the dpbiiq chelate. Thus,
[3]rotaxane 175 was constructed in high yield using click
chemistry.
On the basis of metal templated syntheses, a wide range of
rotaxanes have been constructed and utilized as molecular
machine prototypes, because metal centers are often electroactive, allowing them to induce rearrangements via a metallocalized redox signal, and thus circumventing any potential
diculty associated with the generation of organic radicals.343
In addition, the structure of some transition metal complexes
can be profoundly modied by changing the pH of the medium
or by generating a dissociative excited state, thus allowing some
parts of the compounds to be set in motion using a chemical
signal or a photonic impulse. This part will be discussed in the
following section.
The introduction of the metal-template strategy by Sauvage
represents a very useful synthetic route to prepare rotaxanes
and other MIMs. Recently, Leigh and colleagues described a
rotaxane-forming protocol in which the Cu(I) atom functions
as a catalyst as well as a template and turns over during the
reaction, quite dierent from the reported approaches that
require a stoichiometric quantity of template.344 In this design,
a permanent coordination site is only needed on the
macrocycle; the rest of the interlocked compound is assembled
through functional groups that react together under catalysis by
the metal, which also serves to hold the fragments in position
such that their catalyzed reaction leads to the desired
interlocked product.
The CuAAC reaction345 with mild reaction conditions and
high yield acts as a promising candidate for testing the active
template rotaxane concept.346,347 Taking one of Leighs studies
as an example, simply stirring an equimolar mixture of the
pyridine macrocycle 176a, alkyne 177, azide 178, and
[Cu(CH3CN)4](PF6) and then demetalation with KCN
successfully aorded [2]rotaxane 179 in high yields (Scheme
56).346 The structure of the pyridine-based macrocycle was
systematically varied from the monodentate 176a to bidentate
176b. However, the use of tridentate macrocycles 176c failed to
produce any rotaxane, probably because of the lack of the
vacant coordination sites necessary to bind both azide and
alkyne for the complexes. When the macrocycle 176a to Cu(I)
molar ratio was varied from 1:1 to 10:1, the rate of reaction was
considerably slowed, and [3]rotaxane 180 with two macrocycles and one triazole ring was surprisingly isolated. Such
[3]rotaxane arose from a bimetallic intermediate with two
macrocycles bound to both Cu(I) ions during the formation of
one triazole ring.
Following the CuAAC reaction, which has been successfully
used for the active template rotaxane synthesis, other active
Scheme 57. Pd(II)-Template Synthesis of [2]Rotaxane 182
bidentate macrocycle 176b rst formed, then was transmetalated with a boronic acid, followed by substitution of the
second acetate ligand by an electron-poor alkene to generate
complex 181Pd(II). Migratory insertion of the alkene into the
aryl (or alkenyl)Pd bond resulted in new CC bond
formation through the macrocyclic cavity, capturing the
threaded structure. -Hydride elimination led to poorly
coordinating Pd(0) and release of the metal-free rotaxane
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Very recently, Stoddart and co-workers reported two series

of oligorotaxanes (up to the [20]rotaxane) based on the
reaction of 2,6-pyridinedicarboxaldehyde and tetra(ethylene
glycol) bis(2-aminophenyl) ether with CH2NH2+CH2
containing dumbbell components as templates by the clipping
strategy.19 The NH2+ recognition sites in the axle were
separated by trimethylene bridges or p-phenylene linkers,
respectively (Scheme 59a). The distance between two NH2+
recognition sites in the trimethylene-linked series was designed
to be 3.5 for facilitating ecient [] stacking between
contiguous arene units in the rings of the rotaxanes (Scheme
59b). As a result, a series of [n]rotaxanes up to [20]rotaxane
were isolated in 8898% yields. The eciency of the higher
order oligorotaxanes was improved by the positive cooperativity
resulting from the designed extended [] stacking
interactions.
Besides the above example of rotaxanes with multiple ring
components, a large ring could also encircle several linear
components to form another type of oligopseudorotaxane.86,366
In the following case, the dumbbell component was replaced by
a 3-fold branched component to form a branched rotaxane.223,358362 By using the click methodology, the DNP azide
192 reacted with tris-1,3,5(4-ethynylphenyl)benzene 193 in
the presence of CBPQT4+, leading to the formation of
branched [4]rotaxane 19412PF6 in 72% isolated yield (Scheme
60).358 Because the rings and binding sites in branches are
identical, this type of rotaxane could also be described as a
homorotaxane.
If the three terminal components are designed as macrocyclic
host molecules with large central cavity, three linear molecules
can be threaded by such branched multiple rings to form
another type of rotaxane. On the basis of complexation of a
homotritopic tris(crown ether) and a polymeric paraquat
derivative, a supramolecular triarm star polymer was obtained
via a supramolecular coupling method by Gibsons group
(Scheme 61).72 The axle 196 was designed by introducing a
paraquat moiety at the end of the polystyrene chain, while a
BMP32C10 derivative was reacted with 1,3,5-benzenetricarbonyl trichloride to form a homotritopic host 195. [4]Pseudorotaxane 197 then was prepared with 1:3 stoichiometry
in solution. This work provides a new method for preparing
guest-terminated macromolecular building blocks, which are
very valuable in the fabrication of well-dened macromolecular
architectures by self-assembly.
As compared to the synthesis of homorotaxanes, the
preparation of heterorotaxanes is more challenging due to
their structural complexity. Self-sorting binding is generally
required for selective recognition.103,367 In a pioneering work,
Li and co-workers reported a hetero[3]rotaxane comprising a
tetralactam macrocycle and CBPQT4+ macrocycle as ring
components, driven by hydrogen-bonding and donoracceptor
interactions, respectively.368 Another type of hetero[3]rotaxane
with one stilbene and one cyanine dye as axle components both
threading through the same -CD ring was synthesized by
Anderson and co-workers.176 Wu and co-workers demonstrated
the synthesis of a hetero[4]rotaxane by a threadingstoppering-followed-by-clipping approach.363 Very recently,
an ecient one-pot click reaction was applied for quantitative
emergence of hetero[4]rotaxanes (Scheme 62).364 By mixing
bispropargyl derivative 1992Cl, azide derivative 198Cl, -CD
or -CD, and CB[6] in aqueous solution at 80 C in the molar
ratio of 1:2:1:2, hetero[4]rotaxanes 200a4Cl and 200b4Cl
were obtained very rapidly and quantitatively (>99%). Such
182. In situ reoxidation of the metal with benzoquinone and O2

aorded the rotaxane in 73% yield using only 10 mol % Pd as
the catalyst.
2.9. Synthesis of Oligorotaxanes
On the basis of various wheel-like molecules, a large number of

[n]rotaxanes have been prepared by diversied strategies,
among which oligorotaxanes have more complicated structures
and possibly require more challenging synthetic routes.
Generally there are two types of oligorotaxanes: homorotaxanes
that consist of only one type of macrocycles19,354357 or
axles 138,223,358362 and binding sites, and heterorotaxanes103,363365 that have dierent rings and recognition sites
on the dumbbell-like thread. The [3]rotaxane 52PF6 described
in Scheme 4 is an example of homorotaxanes. These linear
interlocked molecules with multiple rings threaded onto the
same axle containing several binding sites were synthesized by
the capping strategy. Recently, Leigh and co-workers reported a
novel method for the synthesis of homorotaxanes with multiple
rings threading onto a single-binding-site thread by the clipping
strategy (Scheme 58).354 First, through deprotonation of the
Scheme 58. Metal Template Synthesis of Oligorotaxanes
with Multiple Ringsa
Reproduced with permission from ref 354. Copyright 2007 WileyVCH Verlag GmbH & Co. KGaA, Weinheim.
amide groups of a tridentate 2,6-pyridinedicarboxamide

derivative, the metal atom Pd(II) was bound to the ligand to
form complex 184, which interacted with the thread 183 and
subsequently underwent macrocyclization by ring-closing
metathesis (RCM) to generate a saturated palladium [2]rotaxane in 72% yield. After demetalation, the metal-free
[2]rotaxane was obtained in 62% overall yield. This [2]rotaxane
further underwent the process of complexation, macrocyclization, and demetalation to aord the [3]rotaxane in 79% overall
yield. Furthermore, the [4]rotaxane was also obtained under
the same conditions. By using this ecient and eective
strategy, both the number and the order in which macrocycles
are assembled onto a thread can be controlled with
unprecedented precision.
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Scheme 59. (a) Synthesis of Oligorotaxanes with Multiple Rings Based on Hydrogen-Bonding Template; and (b) Cartoon
Representation of [20]Rotaxane 189ga
[2]rotaxanes investigated until now are mostly caused by the

dierent directions of guest insertion as described above.53,370
There are also very few examples resulting from the intrinsic
isomeric property of the host itself.271,371
Pioneering work on isomeric [2]rotaxanes was reported by
Kaifer in 1991,53 in which two isomeric rotaxanes diered in
the orientations of the CD torus with respect to the dierent
terminal groups on the axle component. On the basis of a
similar principle, isomeric phenomena have also been observed
both in [2]pseudorotaxanes and in [3]pseudorotaxanes
incorporating -CD.169 From a theoretical respective, there
should be three isomers in [3]pseudorotaxanes or [3]rotaxanes
with two CD-rings encircling in one axle bearing two dierent
stoppers. However, an unexpected result was found in the case
of a [3]rotaxane with the azo dye derivative threading into two
-CDs.372 This azo dye [3]rotaxane 206 formed as a single
stereoisomer, with the wider rim of both cyclodextrins pointing
outward (Figure 17). This high selectivity of directional isomers
was described as unidirectional threading. A unidirectional
[2]rotaxane 207 was synthesized by Anderson and co-workers
in 2001 with a yield of 96% (Figure 17).373 A space-lling
representation of the energy-minimized structure supported the
experimental result that the wide rim of the hexakis(2,3,6-tri-Omethyl)--cyclodextrin (TM--CD) was over the naphthalene
unit, whereas the narrow rim was over the para-phenylene unit.
For further investigation, Tian and co-workers developed
new methods for controlling the orientation of CDs when
synthesizing a [2]rotaxane-based molecular shuttle (Scheme
64).374376 The origin for the formation of single isomeric
[2]rotaxane 211 was described as follows: when -CD was
mixed with the linear stilbene moiety 208, two [2]pseudorotaxane isomers 209a and 209b formed simultaneously
after 50 min. However, isomer 209a disappeared almost
completely after 36 h. It was indicated that the threading rates
CD-CB[6]-promoted azidealkyne cycloadditions opened the

real possibility of being able to synthesize high molecular
weight polyrotaxanes.
Recently in Lius group, a more complicated hetero[7]rotaxane with twin axles was prepared using B21C7 and
BPP34C10 as the wheel-like components (Scheme 63).365
First, a four-component self-assembly system involving two
macrocyclic polyethers, BPP34C10 and B21C7, and two
secondary ammonium compounds, 201PF6 and 202PF6, was
designed. After mixing all compounds, [2]pseudorotaxane 203
PF6 and [3]pseudorotaxane 2042PF6 with twin axles formed
exclusively. Hetero[7]rotaxane 20510PF6 then was obtained in
42% yield through CuAAC click reaction, in which four
B21C7 rings were stoppered by the outer phenyl groups, while
the central BPP34C10 ring was stoppered by the B21C7 rings.
This strategy provides a good methodology for preparing more
complicated functional MIMs and allows their precise positional control in the structure.
2.10. Isomeric Rotaxanes
Isomeric phenomena are a very interesting and signicant topic

in the area of supramolecular chemistry,369 as is so in the eld
of rotaxanes. In the eld of pseudorotaxanes and rotaxanes, the
cyclic components employed as wheels involve two types: one
is symmetrical, such as crown ethers, cucurbiturils, and
pillararenes; the other is nonsymmetrical, such as cyclodextrins
and calix[6]arenes. In the case of symmetrical macrocycles, if
the two bulky stoppers of a rotaxane are dierent, it may display
isomeric phenomenon, which results in an unsymmetrical
structure and leads to doubling of some of the 1H NMR
signals.322 When a nonsymmetrical macrocycle is used as the
wheel, an axle with dierent terminal groups can insert into the
macrocycle from both rims, thus leading to two isomeric
[2]pseudorotaxanes or [2]rotaxanes. Isomeric phenomena on
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Scheme 60. Synthesis of Branched [4]Rotaxane 19412PF6 Using Click Methodology
on the ring component facilitated the separation of anions from

ion pairs. Therefore, the cationic portions of the axles threaded
almost exclusively from the upper rim. Thus, isomeric
[2]pseudorotaxanes 214a and 214b were yielded in independent ways. By stoppering the other alcoholic OH group with
dierent bulky units, [2]rotaxanes 215a and 215b were
subsequently produced through the snapping method (Scheme
2).
Furthermore, with the same host system, to evidence
possible eects of the structural features of the axles on the
threading direction into the wheel and to implement the
straightforward synthesis of orientational rotaxane isomers, a
family of nonsymmetrical axles with a stopper at one side and
the other side with either an ammonium, a hydroxy, or a methyl
headgroup were designed and synthesized by Arduini and coworkers.378 A detailed thermodynamic and kinetic study was
carried out and revealed that all axles threaded the wheel from
the upper rim for kinetic reasons at room temperature;
conversely, the axle with an ammonium headgroup was capable
of entering the cavity from the lower rim at 340 K under
thermodynamic control.
Besides CD-induced or calix[6]arene-induced isomeric
pseudorotaxanes, a DB24C8-based cryptand also induced
dierent spatial arrangements of hostguest complexes, as
reported by Huang, Gibson, and co-workers.379 In this case,
of stilbene unit through the wide rim and through the narrow
rim were not much dierent, but the dethreading rate of the
former [2]pseudorotaxane 209a was much faster than that of
the latter, giving mostly the thermodynamically stable isomer
209b. Finally, the resulting [2]pseudorotaxane 209b underwent
Suzuki coupling with the boronic acid 210 to give the
unidirectional [2]rotaxane 211.
Not only nonsymmetrical cyclodextrins, but nonsymmetrical
calix[6]arene derivatives, with a truncated cone structure, have
been used to construct unidirectional [2]pseudorotaxanes and
[2]rotaxanes by Arduini and co-workers.232,370,377,378 In 2003,
unidirectional [2]pseudorotaxanes based on
triphenylureidocalix[6]arene were initially reported.370 It was
shown that the nonsymmetrical axle accessed the calixarene
cavity only through the wider rim. On the basis of this
discovery, unidirectional [2]rotaxanes 215a and 215b,
described as isomeric compounds, could be highly selectively
synthesized, respectively (Scheme 65).377 Axles 213a and 213b
incorporated the paraquat unit as interactional sites, one
stopper at one side (213a, diphenylacetyl unit; 213b,
dicyclohexylacetyl unit) and an alcoholic OH group for further
stopping at the other side. The axles existed as tight ion pairs,
so it was dicult for them to thread into the cavity of
calix[6]arene during the initial process of pseudorotaxane
formation. The hydrogen-bonding ability of ureido NH groups
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Scheme 63. Preparation of a Hetero[7]rotaxane 20510PF6a
Scheme 61. Schematic Illustration of the Formation of a

Supramolecular Triarm Star Polymera

Chemical Society.
Scheme 62. Synthesis of Hetero[4]rotaxanes 200a4Cl and

200b4Cl by One-Pot Click Reaction
In the literature, isomeric phenomena of [2]rotaxanes are

mostly caused by the direction of guest insertion. When the
guest is symmetrical, can isomeric [2]rotaxanes still form by the
eect of the host? This is also an interesting question to
explore. Recently, Chen and co-workers designed and
synthesized a series of squaraine-based [2]pseudorotaxanes
and [2]rotaxanes incorporating triptycene-based tetralactam
macrocycles.380 In particular, isomeric [2]pseudorotaxanes and
[2]rotaxanes were obtained from both the linking modes of
triptycene derivatives and the directions of the guest insertion
(Scheme 67). Consequently, in the case of [2]rotaxanes 222,
three isomers were simultaneously obtained from one reaction.
It provides a new route to form isomeric [2]rotaxanes through
the template synthetic process.
Sequence isomerism in rotaxanes also exists when the
nonsymmetrical thread is encircled by constitutionally dierent
how the guests threaded into the cavity of the host was
determined by the terminal N-substituents. As seen from
Scheme 66, cryptand 216 formed 1:1 inclusion complexes
218ac with three paraquat derivatives 217a,b and 40. Their
association constants determined in acetone by using a UVvis
titration method were 1.0 105 M1 for 218a, 1.2 105 M1
for 218b, and 5.0 103 M1 for 218c, respectively. It was
conrmed by X-ray crystal structures that methyl-substituted
paraquat derivatives 217a and 217b bound cryptand with
similar T-type inclusion complexation conformations, while the
nonmethyl-substituted paraquat derivative 40 bound the
cryptand with the pseudorotaxane-type complexation conformation. Therefore, the conformation of the hostguest
complex could be controlled by simple substitution.
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nonsymmetrically with a pyridine group on one side and an

alkane chain on the other side, two dierent macrocycles could
be positioned on the thread with a special sequence, which was
determined by the structure of the starting [2]rotaxane. When
[2]rotaxane 223a was used, the ring containing an isopropyl
ether on the 4-position of the pyridine group would be nally
located at the pyridine side of the axle, while [3]rotaxane 225b
with the contrary sequence of the rings was produced if the
starting material was [2]rotaxane 223b. The rings in such
[3]rotaxanes were suciently small and rigid that the sequence
was maintained mechanically. This synthetic strategy can be
extended to add multiple dierent rings to a rotaxane thread in
any desired order, and thus enable the synthesis of single
isomeric rotaxane of higher order with a predened macrocycle
sequence.
2.11. Rotaxane-Related HostGuest Complexes Based on
Molecular Tweezers and Clips
Figure 17. Representation of azo dye [3]rotaxane 206 and [2]rotaxane

207 as single stereoisomers.
Before rotaxane formation, there exist two types of supramolecular complexes considered as intermediates driven by
noncovalent intermolecular interactions (Scheme 69). Through
the capping or snapping methodology, a pseudorotaxane
complex is initially and necessarily aorded, the coconformations and movements of which have already been widely
investigated. When the clipping method is involved, the
supramolecular intermediate forms with a tweezer- or
clipping-like component encircling a dumbbell-like component,
which we refer to as the clipping complex. Such complex also
shows its unique conformation and association/dissociation or
shuttling motion under external stimuli. Although various
molecular clips and tweezers and their hostguest chemistry
have been reported so far,382384 only a few investigations have
been focused on clipping complexes containing dumbbell-like
guests.385
To study the synergistic eects generated by multiple arene
arene interactions, Klarner and co-workers designed and
synthesized a series of tetramethylene-bridged molecular
tweezers 226 and 227, trimethylene-bridged molecular clip
228, and dimethylene-bridged clips 229232 (Figure 18).385
All of these structures exploit multiple -stacking interactions in
a positively cooperative manner, and demonstrate selective
binding of cationic or neutral guests that bear acceptor groups.
The tweezers 227 and clips 228232 bind aromatic guest
molecules preferentially via CH and interactions,
whereas tweezers 226 prefer to bind alkane chains of aliphatic
guest molecules inside their cavities via CH interactions.386,387 Because of their belt-shape structures and energy
requirement for bond angle distortions, these molecules are
well preorganized but present small exibility in tuning the
cavity sizes, which endow the hostguest complexes with
particularly dynamic properties.
Molecular tweezer 227b, comprising one naphthalene and
four benzene components bridged by four methylene units,
forms a stable 1:1 complex with dendrimers 233ad containing
a bipyridinium core, both in solution and in the gas phase
caused by charge-transfer interactions (Scheme 70).388,389 Such
hostguest formation caused the quenching of the tweezer
uorescence. The association constants measured by uorescence titration experiments in dichloromethane or a mixture
of dichloromethane/acetonitrile were of the order of 104 M1,
which decreased dramatically in polar acetone solution. Besides,
increasing dendrimer generation also resulted in a decrease of
association constants. Cyclic voltammetry experiments in-
Scheme 64. Formation of Unidirectional CD-Based

[2]Rotaxane 211
macrocycles.103,354 Leigh and co-workers recently reported

such a pair of [3]rotaxane sequence isomers (Scheme 68).381
On the basis of the strategy described in Scheme 58,354
[3]rotaxanes 225a and 225b with two dierent macrocycles
and one nonsymmetrical thread were obtained under the
process of coordination, macrocyclization, hydrogenation, and
demetalation. Because the dumbbell component was designed
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Scheme 65. Formation of Unidirectional Calix[6]arene-Based [2]Rotaxanes 215a and 215ba
(i) Toluene, reux; (ii) Cy2CHCOCl, toluene; (iii) Ph2CHCOCl, toluene. Cy = cyclohexyl.
Scheme 66. Chemical Structures of Cryptand 216 and Paraquat Derivatives 40 and 217a,b and Cartoon Representations of
Their HostGuest Complexes 218aca
dicated that such complexes could be reversibly assembled/

disassembled by electrochemical stimulation. Further investigation concluded that shuttling of the tweezer from one
pyridinium ring to another happened rapidly (G < 10 kcal/
mol).390 Furthermore, the addition of Bu4NPF6 to the solutions
of the complex in low-polar solvents caused an unfolding
change in dendrimer conformation, which stabilized the

complex with higher association constants.391
Besides polyaromatic tweezers, TTF-side-walled molecular
clip 235 was designed and allowed the shuttling motion of a
pH-controllable [2]rotaxane 236 to be monitored by the naked
eye (Scheme 71).392 By mixing solutions of colorless
[2]rotaxane 2362PF6 and yellow molecular clip 235, the
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Scheme 67. Formation of Isomeric [2]Rotaxanes from Both the Linking Modes of Triptycene Derivatives and the Directions of
the Guest Insertiona
bonding interactions to create a stable species in solution.

While chemically interesting in their own right, pseudorotaxanes are dynamic species and may dissociate when subjected to
changes of solvent and/or temperature, or addition of
appropriate external stimuli, such as chemical, electrochemical,
and/or photochemical stimuli. The stimuli-responsiveness of
the association/dissociation mobility of pseudorotaxanes will be
summarized in detail.
3.1.1. Solvent Eects on Association Constants. The
solvent eects in hostguest chemistry can hardly be neglected.
The solvation interactions always participate in competition
with the complexation between host and guest molecules in
solution.393395 Hydrogen bonding is considered as a powerful
driving force to form pseudorotaxane-type complexes. However, polar solvents, particularly water, can aect hydrogenbonding interactions to a large degree.395 The increase of Ka
values for this type of complexes depends on the decrease of
the Gutmann donor numbers of the solvents. For example,
DB24C8 forms supramolecular complexes with dialkylammonium salts in a number of dierent solvents.80 In CHCl3, the Ka
value is the highest, whereas no complex formation is observed
in DMSO. On the basis of the above phenomenon, most
pseudorotaxane complexations driven by hydrogen bonding
have been investigated in nonpolar solvents.286,316 In
conclusion, it is essentially meaningless to discuss the
magnitude of binding constants without mention of solvents
and impossible to compare binding constants or even relative
anities across dierent solvent media.
solution turned green, suggesting the formation of [2]rotaxane/

clip complex (235236-H)3PF6 with a charge-transfer band (
= 709 nm). The association constant (Ka) in CD3CN/CDCl3
(5:1) was determined to be 4100 400 M1, based on a 1H
NMR spectroscopic dilution experiment. This complex could
be dissociated by addition of Et3N and was reformed upon
introduction of CF3CO2H. Without the clip molecule, the
switching of the macrocyclic unit between the NH2+ unit and
the bipyridinium moiety also happened by tuning the pH of the
solution with little color change. It was concluded that such a
molecular clip provided a visible way for monitoring the
switchable process.
3. STIMULI-RESPONSIVE MOLECULAR MOBILITY OF

PSEUDOROTAXANES
A pseudorotaxane is a supramolecular system composed of a
thread-like species inserted through the cavity of a macrocycle.
Because there are no stoppers at the ends of the thread,
dissociation of the complex is easy in solution and the
pseudorotaxane is always equilibrated with the free molecular
components (Scheme 72). In addition to the main association/
dissociation mobility, shuttling of the wheel along the bistable
axle is another type of mobility for pseudorotaxanes. In this
section, these two types of mobilities and the functions of
pseudorotaxanes based on these mobilities will be discussed.
3.1. Association/Dissociation Mobility
Generally, the threading of a linear component through the

macrocycle is driven thermodynamically by noncovalent
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Scheme 68. Parallel Synthesis of [3]Rotaxane Sequence Isomers 225a and 225b
Scheme 69. Complexes for the Construction of Rotaxanes:

Pseudorotaxane and Clipping Complex
The hydrophobic eect is another case involving solvent

inuence.394 It generally relates to the exclusion of guests,
usually from polar solvents, particularly water. It is of crucial
importance in the binding of organic guests by cyclodextrinand cucurbituril-based hosts in water. Because these host
cavities are hydrophobic, water inside the cavity does not have
strong interactions with the host walls and is therefore of high
energy. Organic guests, which can thread into the cavity of the
host to form a complex, result in less disruption to the solvent
structure and hence lower the overall free energy.
3.1.2. Temperature Eect: Slippage or Deslippage?
Temperature can aect the association process not only from
Figure 18. Chemical structures of molecular tweezers 226 and 227

and molecular clips 228232. Reproduced with permission from ref
its binding constant, but also from the association/dissociation

rate of its complex. The most outstanding example of the
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Scheme 70. Cartoon Representation of the Assembly/

Disassembly Process for the Clipping Complex 2342+a
Scheme 72. Two Types of Molecular Mobilities of

Pseudorotaxanes
component to form a rotaxane. When the solution is cooled to

ambient temperature, the axle cannot slip out of the ring
because of the high energy barrier (Figure 19).396 To make the
Scheme 71. Formation of the [2]Rotaxane/Clip Complex

and Corresponding pH Controllable Switchinga
Figure 19. Schematic representation of the formation of rotaxane-like

entities using the slippage approach.
threaded molecules kinetically stable under the appropriate

conditions, it is essential to modify the termini of the axle with
appropriate stoppers: a too small stopper makes the host and
guest complex as a pseudorotaxane, and a too big stopper
prevents slipping after heating.
In 1993, Stoddart and co-workers used this strategy to
prepare rotaxanes in high yields up to 87% between -electronrich hydroquinone-based macrocycles and -electron-decient
bipyridinium-based dumbbells, which could not be obtained by
the capping method (Scheme 73).398 A range of 4,4bipyridinium dications 237ad were prepared, in which the
size of the stoppers varied systematically. As a result, rotaxanes
238ac were isolated after heating at 60 C for 10 days.
However, the stoppers of 237d were too big to permit slipping
to occur at a preparatively useful rate. Thus, no rotaxane
formed.
To gain further understanding of the mechanism and the size
complementarity requirements associated with the slippage
approach to rotaxanes, several hostguest systems such as electron-decient bipyridinium-based macrocycles and electron-rich hydroquinone-based dumbbells,397 DB24C8 and
secondary dialkylammonium ions,396 and the tetralactam
macrocycles and their diester axles399 have been exploited for
these investigations. Besides its size, complex molecular
structure, and the high exibility of the mechanical bond, the
Reproduced with permission from ref 392. Copyright 2006 Royal

Society of Chemistry.
temperature eect is the formation of rotaxanes based on the

slippage method.396400 In this method, the macrocycle and the
thread molecule are independent at room temperature without
any interactions, whereas after they are heated together in
solution, the high temperature will provide enough energy for
the axle with appropriate stoppers to slip into the ring
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Scheme 73. Synthesis of Rotaxanes 238ac Using the Slippage Approach
deslipping reaction of a rotaxane is very sensitive even to

extremely small changes in the molecular architecture, and the
steric demand of its components can aect the process.400
These features provide a viable and alternative synthetic
procedure for the construction of larger rotaxanes and
polyrotaxanes based on elevating temperature.
3.1.3. External Stimuli. Supramolecular complexes such as
pseudorotaxanes are attractive to scientists not only due to their
topological importance, but also because of their applications in
the construction of articial molecular machines, which respond
to appropriate external stimuli. By modulating the attractive/
repulsive forces between the cyclic and linear components of
pseudorotaxanes, control of the association/dissociation
process can be readily and reversibly achieved. Several methods
have been employed for this purpose, including chemical
stimuli,401 photochemical stimuli,402 redox stimuli,403 or other
control elements.404
3.1.3.1. Chemical Stimuli. The threading and dethreading of
a [2]pseudorotaxane can be induced by chemical stimuli, such
as pH control,405411 anion control,306,307,412,413 cation
control,414417 or addition of other competitive host or guest
molecules.418,419 It was known that the association and
dissociation of the complex between DB24C8 and secondary
ammonium salts could be chemically controlled by pH.79 For
-electron-rich crown ether 239 and its guest -electrondecient 2,7-dibenzyldiazoniapyrene dication 240, the motion
of the relevant [2]pseudorotaxane could also be induced by
adding acid and base reagents.420 The association constant of
the complex 239240 was about 3 105 M1 in MeCN. The
hexylamine molecule, which forms a 2:1 complex with 240 with
an association constant of the order of 108 M2, was used to
unthread the [2]pseudorotaxane 241 (Scheme 74). Addition of
triuoroacetic acid (TFA) resulted in the disruption of the
interactions between hexylamine and 240 by protonation of the
amine and rethreading of the [2]pseudorotaxane between 239
and 240.
Another example of pH-controlled complexation systems is a
stable ternary complex 242 formed by the triptycene-based
cylindrical macrotricyclic host 61b, electron-decient diquat,
and electron-rich benzidine guest, which is stabilized not only
by a charge-transfer (CT) interaction between electron-rich
and electron-decient guests but also by the face to face -
Scheme 74. Chemically Driven Unthreading and

Rethreading of the [2]Pseudorotaxane Incorporating Crown
Ether 239
stacking interactions between the host and the guests (Scheme

75).421 Upon addition of TFA, the benzidine was protonated to
form a cationic diammonium ion, which dethreaded from the
two lateral DB24C8 cavities of cylindrical macrotricylclic host
to form another type of 1:1 complex 243. Consequently, the
diquat cation was extruded and the ternary complex
decomposed. Furthermore, addition of tributyl amine to the
above system led to a reversible rethreading process.
The manipulation of the above pseudorotaxane systems was
based on changes of the guest species in response to chemical
reagents. A pH-responsive example based on changes of the
host species was described by Gibson and co-workers.422 Their
studies showed that the complex of the pyridine-containing
cryptand host 39e and the paraquat guest had a 1:1
stoichiometry in solution (Scheme 76). Addition of TFA
resulted in the protonation of the pyridyl nitrogen atom on the
cryptand host and subsequently the decomplexation of the
cryptand host and paraquat guest. The complexation process
could be recovered by addition of triethylamine. Furthermore,
Gibson and co-workers also synthesized bis(m-phenylene)-32crown-10-functionalized poly(propyleneimine) dendrimers of
the rst and third generations and investigated their pHresponsive complexation with paraquat diol.423 Interestingly,
protonation of the dendrimer skeleton resulted in enhanced
binding due to expansion of the structure.
The above examples are based on the pH control. Anions
have also been used as a control to modulate pseudorotaxane
formation. As described in Scheme 44, by coordination with
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Scheme 75. An AcidBase Controlled Selective Complexation Process Based on Macrotricyclic Host 61ba
Scheme 76. An AcidBase Controllable Cryptand/Paraquat

[2]Pseudorotaxane via Protonation/Deprotonation of Host
39ea
Scheme 77. (a) Formation of Cryptand/Paraquat-Based

Pseudorotaxane 24440; and (b) A Cation Controllable
Switch Based on [2]Pseudorotaxane 24440a

Chemical Society.

acceptor is to add photosensitizers. The pioneering work in this

respect was reported by Stoddarts group.424 The dethreading
of a pseudorotaxane based on a tetracationic cyclophane and a
linear molecule containing DNP group was observed by adding
9-anthracenecarboxylic acid as a photosensitizer (Scheme 78).
Upon being sensitized by light, 9-anthracenecarboxylic acid
donated an electron to the CBPQT4+ ring to generate a
diradical dication species in the presence of the sacricial
reagent triethanolamine, which prevented the back electron
transfer process. The complexation was recovered by
introduction of air into the system, which regenerated the
CBPQT4+ ring and reproduced the original uorescence
spectrum.
Further investigation on a second-generation light-driven
association and dissociation process of a pseudorotaxane has
been subsequently developed. In this system, the photosensitizing component was directly incorporated into the pseudorotaxane suprastructure.425 In addition to two 4,4-bipyridinium
electron-acceptor units, the cyclophane 2454+ also contained a
2,2-bipyridine coordinating ligand, which was coordinated to
[Re(CO)3Cl] to obtain the cyclophane [Re(CO)3245Cl]4+
incorporating a metal-based photosensitizer component
(Scheme 79). When the wheel-like component and a DNP
derivative were 1:1 mixed together in solution, a [2]-
amide NHs, chloride anion was used as a template for a lactam

macrocycle-based [2]pseudorotaxane. Removal of chloride led
to dissociation of the complex. In addition to anions, Gibson
and co-workers developed a new cation mechanism for the
control of molecular motion a few years ago.414 Formation of
the cryptand/paraquat-based pseudorotaxane 24440 could be
switched o and on by adding K+ and 18C6, respectively
(Scheme 77a). The corresponding binding constant was
determined to be 1.4 104 M1. Stronger binding anity
was observed for cryptand 244 and KPF6, which provided a
new mechanism for the molecular motion control by K+. After
addition of K+ to a solution of complex 24440, K+ displaced
paraquat diol 40 from the cryptand cavity, leading to a color
change from yellow-orange to colorless (Scheme 77b).
Furthermore, addition of 18-crown-6, which binds K +
preferentially, allowed the colored cryptandparaquat complex
to reform.
3.1.3.2. Photochemical Stimuli. Pseudorotaxanes based on
donoracceptor interactions can be destabilized and even
dissociated by reduction of the electron acceptor or oxidation
of the electron donor. One method for reducing the electron
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Scheme 78. Light-Induced Dethreading of a Pseudorotaxane

Based on CBPQT4+ Using 9-Anthracenecarboxylic Acid As a
Photosensitizer
Scheme 80. Electrochemically Induced Molecular Motions

in Pseudorotaxanes Incorporating CBPQT4+ and 1/
5DN38C10 as Ring Components and the TTFs in Dierent
Oxidation States as Axles
on the fact that CB[8] strongly associates the dimer of the

paraquat-containing dendrimers in their one-electron reduction
state (Scheme 81).429 The formation of [2]pseudorotaxanes
Scheme 81. Electrochemical Control of the CB[8]-Induced
Dimerization of a Paraquat-Containing Dendrimera
Scheme 79. Schematic Representation of the Light-Induced
Disassembly of a [2]Pseudorotaxane Incorporating the
Photosensitizing Motif in the Macrocycle Ring
pseudorotaxane formed because of donoracceptor interactions. Light excitation of the cyclophane of the pseudorotaxane
caused transfer of an electron from the metal center to one of
the 4,4-bipyridinium units in the ring, thereby decreasing the
noncovalent-bonding interactions responsible for the formation
of the pseudorotaxane. Disassembly occurred in the presence of
a sacricial reductant. Furthermore, when oxygen was allowed
to enter the irradiated solution, the reduced host was promptly
reoxidized and the pseudorotaxane was obtained again.
3.1.3.3. Electrochemical Stimuli. Both the tetracationic
cyclophane and the TTF unit can behave in charge-transfer
complexes as a donor or an acceptor depending on their
dierent oxidation states. Therefore, pseudorotaxanes based on
these two components can be controlled by electrochemical
stimuli.426,427 For TTF, there exist specically three stable
forms, TTF(0), TTF+, and TTF2+. Neutral tetrathiafulvalene
(TTF(0)) acts as a -electron-donating (ED) guest when it
complexes with the -electron-accepting (EA) CBPQT4+.
Dication TTF2+, with EA property, binds strongly within the
cavity of the ED macrocyclic polyether 1,5-dinaphtho[38]crown-10 (1/5DN38C10). However, the radical cation TTF+
can not be bound by either of the hosts. On the basis of the
three states, a three-pole supramolecular switch with CBPQT4+
and 1/5DN38C10 as hosts and TTF as the guest was designed
and developed (Scheme 80).428
Another example of the electrochemical stimuli-induced
association/dissociation mobility of pseudorotaxanes is based
incorporating paraquat-terminated dendrimers as the axles and

CB[8] as the ring component was initially monitored by
electronic absorption spectroscopy. Reduction of a solution of
the dendrimers and CB[8] led to extensive dimerization.
Although the increase in the size of the dendrimers may be a
factor that hinders their dimerization, electrostatic interactions
play a much more important role. The third-generation
dendrimer 246 dimerized in a yield of 50% with their paraquat
radical cations inside the cavity of the CB[8] ring.
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3.1.3.4. Multi-Stimuli. As the above examples exemplied,

the association/dissociation mobility of the [2]pseudorotaxanes
consisting of CBPQT4+ and DNP derivatives can be controlled
by photochemical stimuli. Additionally, the complexation of
CBPQT4+ and DNP derivatives can also be modulated by
electrochemical stimuli.430 There are many other cases where
the supramolecular systems can be controlled by two or more
stimuli. In an example reported by Credi and co-workers, the
formation of a [2]pseudorotaxane incorporating
triureidocalix[6]arene as the ring component was controlled
via protonation/deprotonation of the monoalkyl-substituted
4,4-bipyridine cation via addition of acid or base.431 Although
this system was photoinactive, this process could be controlled
by adding a photosensitive reagent (Scheme 82). Spiropyran
Figure 20. Photoinduced electron transfer in a [3]pseudorotaxane that

can be assembled/disassembled by three dierent external inputs.
Chemical Society.
Scheme 82. Control of Threading/Dethreading Process in

Paraquat-Containing Pseudorotaxane by Means of LightInduced Proton Exchangea
secondary dialkylammonium-ion center and a paraquat unit,

were incorporated into the wire-type component 248-H3+ to
thread into the DB24C8 socket of 2472+ and the cavity of 1/
5DN38C10 239, respectively. It was conrmed that reversible
association/dissociation of the two plug/socket systems 2472+
248-H3+ and 248-H3+239 could be controlled independently
by acid/base and redox stimulation. In the fully connected
three-components system, light excitation of the [Ru(bpy)3]2+
unit of component 2472+ was followed by electron transfer to
the paraquat unit in component 248-H3+, which was plugged
into component 239. Its operation was governed by three
dierent types of stimuli (light, acid/base, redox), and its
behavior could be monitored by changes in one electrochemical, two light-emission, and two light-absorption signals.
Besides the main association/dissociation mobility, shuttling of

the wheel along the bistable axle is another important type of
mobility for pseudorotaxanes. In 2000, Kim and co-workers
reported a pseudorotaxane-based shuttling process (Scheme
83).433 The system consisted of CB[6] as the bead and
Scheme 83. A Fluorescent, Reversible [2]PseudorotaxaneBased Molecular Switch
a

Chemical Society.
photochrome, whose acidbase properties could be photocontrolled, was selected for this mission. Upon being exposed
to visible light irradiation, the merocyanine compound
underwent cyclization to release a proton, which further
induced protonation of the monoalkylated 4,4-bipyridine cation
axle and formation of the [2]pseudorotaxane. The reversible
process was triggered by heating. Upon heating, the spiropyran
skeleton absorbed a proton from the dicationic axle to undergo
a ring-opening reaction. Thus, the [2]pseudorotaxane decomposed. This is a nice example wherein pseudorotaxane
formation can be controlled by triple stimuli of acid/base,
heat, and light.
Another example of multi-stimuli-triggered systems is
involved with a [3]pseudorotaxane consisting of three
components. It can mimic, at a molecular level, the function
of a macroscopic electrical extension cable (Figure 20).432 The
[Ru(bpy)3]2+ unit on component 2472+ played the role of a
power source under light excitation, and the DB24C8 motif
fullled the function of a socket. Two moieties, including a
uorenyltriamine as the string. When all of the nitrogen atoms

of the string were protonated, CB[6] resided at the protonated
diaminohexane site, because of formation of a more stable
complex. Upon deprotonation of the aniline nitrogen (pKa =
6.7), CB[6] migrated to the diprotonated diaminobutane site
because the binding of CB[6] with the monoprotonated
diaminohexane was weaker. The process could be manipulated
several times by addition of acid and base alternately. The
switching of CB[6] from one site to the other in the string was
easily detected by changes in color and uorescence with high
sensitivity. Besides CB[6], pH-controlled shuttling motion also
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happened on a [2]pseudorotaxane self-assembled from CB[7]

and paraquat moiety.434
Triggered by electrochemical stimuli, a CB[7]-based [2]pseudorotaxane showed the shuttling movement of the ring
along a dicationic axle from the central binding site to the
terminal ferrocenyl group (Scheme 84).435 Complexation
Scheme 85. Photo-Controlled Shuttling Mobility of a

[4]Pseudorotaxane Based on -CD and CB[7]
Scheme 84. Shuttling Mobility of a CB[7]-Based

[2]Pseudorotaxane Controlled by Chemical Stimulia
and showed favorable uorescence emission in the presence of

(Figure 21a).26 Another method for the formation of
D-glucose

Chemical Society.
between the guest 250 and CB[7] was quantitative due to

the remarkably high association constant (Ka > 1012 M1) of
CB[7] with the ferrocenyl unit. Upon oxidation of the
ferrocene center, the complex was signicantly destabilized,
and CB[7] shuttled from one of the terminal binding sites to
the central binding site. The system takes advantage of
hydrophobic, ion-dipole, and electrostatic forces in reversibly
controlling the shuttling movement of CB[7].
Photochemically stimulated shuttling was also observed with
a more complicated [4]pseudorotaxane system.436 Tian and coworkers reported a supramolecular complex based on -CD
and CB[7] and investigated the shuttling movement by induced
circular dichroism (ICD) experiments. The linear compound
251 (Scheme 85) contained an azobenzene moiety and two
paraquat units, providing the binding sites for both -CD and
CB[7], respectively. The E/Z photoisomerization of the
azobenzene unit by irradiation of the aqueous [4]pseudorotaxane at 360 nm resulted in the shuttling of the CD ring away from the azobenzene unit. This change was
shifted back reversibly by irradiation of the solution at 430 nm.
Meanwhile, thermally induced shuttling motion of the -CD
ring was also detected by variable-temperature ICD measurements.
Figure 21. Fluorescent sensors based on [2]pseudorotaxanes.
pseudorotaxane-type uorescent receptors is to functionalize

the macrocyclic unit with a uorescent signaling element and
consider it as a receptor for linear guest molecules. For
example, in recently reported work, by modifying a pillar[5]arene host with a pyrenyl uorophore via CuAAC click
chemistry, the sensor 254 for 1,6-hexanediamine was obtained
(Figure 21b).285 In this example, 1,6-hexanediamine acted both
as an axle of the pseudorotaxane and as a sensor guest
molecule.
3.3.2. Molecular Logic Gates. The design and construction of molecular systems that respond to chemical and/or
photonic inputs, in accordance with logic-gate behavior, have
attracted considerable attention.440 Stimuli-responsive pseudorotaxanes and rotaxanes are ideal candidates for molecular logic
gates.420,441 YES and NOT single-input gates are the simplest
logic devices. Various molecular systems can perform such
operations.442,443 To perform more complex logic operations,
carefully designed multicomponent chemical systems are
needed. One of the successful examples is a [2]pseudorotaxane-type XOR logic gate reported by Balzani and
co-workers.25 The [2]pseudorotaxane was constructed by
association of 2,3-dioxynaphthalene crown ether 256 and 2,7-
3.3. Functions of Pseudorotaxanes
3.3.1. Fluorescent Sensors. Pseudorotaxanes may be

viewed as prototypes of molecular machines because of their
reversible assembly/disassembly and shuttling movement under
external stimuli. In some cases, their photophysical properties
are inuenced along with the kinetic process, making them
sensitive analytical tools in many areas.437439 They can be used
as chemical sensors when uorescent signaling elements are
involved. For example, a -CD derivative bearing a phenylboronic acid residue formed a pseudorotaxane-type complex
with 1-heptyl-4-(4-dimethylaminostyryl) pyridinium, and this
supramolecular complex was an excellent host for saccharides
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Both processes caused a strong increase of emission intensity at

343 nm. It was concluded that the chemical system showed the
input/output relationships indicated by the truth table of the
XOR logic gate. Therefore, the operation of the chemical input
and uorescent output can be considered as an XOR logic gate
at the molecular level.
3.3.3. Molecular Switches. The threading/dethreading
movements of pseudorotaxanes have been used to construct
molecular switches for modulating the properties of supramolecular systems.444448 For example, a lanthanide complex
containing three DB24C8 macrocycles binds dialkylammonium
derivative 258 to form tris[2]pseudorotaxane system [Tb2573
2583] (Scheme 87).446 The luminescence of the lanthanide
coordination complex was completely quenched due to
photoinduced electron transfer (PET) from the ferrocene
moiety of 258 to the pyridine-2,6-dicarboxylic acid 257. Upon
addition of KPF6, the dialkylammonium cation in DB24C8 was
replaced by K+ and the PET process was suppressed; thus the
quenched lanthanide emission was restored. To check the
reversibility of this process, 18-crown-6 was added. It caused
the quenching of luminescence again. This work demonstrated
a new strategy for the fabrication of reversible switches through
electron transfer.
Recently, chemical switches were applied to retain their
activities when attached to metal nanoparticles (NPs).448 A
variety of metal NPs, such as Au, Pt, and Pd NPs, functionalized
with linear -electron-rich recognition sites such as TTF were
prepared. On the basis of the charge-transfer interaction
between TTF and CBPQT4+, the pseudorotaxane complex
formed on the NP surface (Scheme 88). The CBPQT4+ ring
associates or dissociates with the metal NPs triggered by
electrical stimuli. Their switching movement was veried by
potential measurements and CV, which provided the potential
application in the assembly of responsive, nanostructured
materials.
3.3.4. Other Molecular Machines. Switchable [2]pseudorotaxanes play a very important role in the construction
of molecular switches, logic gates, sensors, as well as other
molecular machines.449,450 In 2003, Kim and co-workers
successfully designed and constructed a [2]pseudorotaxanebased molecular loop.451453 In this report, hexamethylenebridged bisparaquat 259 underwent a large reversible structural
change from linear to loop by electrochemical and photo-
dibenzyldiazapyrenium dication 240, in which the electrondecient diazapyrenium unit was sandwiched between two
electron-rich 2,3-dioxynaphthalene units of 256 (Scheme 86).
Scheme 86. Schematic Representation of an XOR Logic Gate
Based on the Threading/Unthreading Pattern of the
Pseudorotaxane 256240
Upon addition of tributylamine, the [2]pseudorotaxane

disassociated due to the formation of a more stable 1:2
complex between 240 and the amine. Subsequent addition of
TFA unlocked the axle compound from the 240B2 (B =
tributylamine) adduct and allowed rethreading between 256
and 240 to form the [2]pseudorotaxane 256240 again.
Furthermore, the unthreadingrethreading cycle could also be
performed by reversing the order of the two inputs. First,
addition of TFA caused the complexation between crown ether
256 and H+, and further unthreading of [2]pseudorotaxane;
then addition of tributylamine unlocked crown ether from 256
H+, allowing rethreading to give back the [2]pseudorotaxane.
Scheme 87. Schematic Representation of a Reversible Luminescent Lanthanide Switcha
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of 259 with a linear structure was approximately 28 18 ,

whereas that of 259 with a loop structure was only about 15
18 . Along with this work, a molecular loop lock, which acted
as a redox-driven molecular machine, was fabricated (Scheme
89b).452 Linear molecule 260 contained both a naphthalen-2yloxy unit and a paraquat unit. These two units formed a
charge-transfer complex inside CB[8]. Therefore, the treatment
of 260 with CB[8] in water resulted in the formation of stable
1:1 complex 261. After addition of another guest paraquat and
being triggered by electrochemical stimuli, paraquat motifs in
both guests became radical cations. Because CB[8] strongly
associated with the dimer of the one-electron-reduced paraquat
unit, a ternary [3]pseudorotaxane 262 was obtained. In this
process, the paraquat molecule acted as a key, which could
open the lock-like molecular loop 261 encapsulated in CB[8].
Another function of pseudorotaxanes based on the
threading/dethreading process was to control molecular rotary
motion.454 The design was based on the fact that a secondary
dialkylammonium ion (R2NH2+) threads into the cavity of
DB24C8. Under neutral conditions, the system cis-263 rotates
freely (Scheme 90); after addition of acid, a self-complexing
[1]pseudorotaxane molecular system cis-263-HPF6 formed.
The hydrogen-bonding interactions between the R2NH2+ unit
and the DB24C8 macrocycle were strong enough to lock the
structure, which prevented rotation. Further deprotonation by
adding base led to the unlocked state of the motor cis-263.
Thus, control of the mechanical motion at the single-molecule
level was achieved. This study represents a good way to
fabricate more advanced molecular devices.
Scheme 88. Reversible Transformation of the

Pseudorotaxane-Type Complexes Attached to the Metal
NPsa

Chemical Society.
chemical stimuli (Scheme 89a).451 The linear guest 259 and

CB[8] initially formed stable [2]pseudorotaxane CB[8]259
Scheme 89. (a) An Electrochemically Triggered Molecular
Loop; and (b) Formation of a Molecular Loop Locka
4. STIMULI-RESPONSIVE MOLECULAR MOBILITY OF

ROTAXANES
Rotaxanes, acting as the most fundamental MIMs, envisage
particularly two types of interesting molecular motions:
shuttling of the ring along the axle, and rotation of the ring
around the axle (Figure 22). Thus, rotaxanes are good
prototypes for the construction of both shuttling and rotary
molecular devices.
4.1. Rotational Mobility
Under the inuence of external stimuli, the mechanical motion

within the rotaxanes can be addressed, and to some extent
controlled. In this section, we pay attention to the rotational
mobility of the wheel around the axle. These systems with
rotational motion represent a rst step toward the elaboration
of rotary motors455,456 at the molecular level.
First, metalationdemetalation of the central coordination
site is considered as an eective way to control the rotation of
the wheel. On the basis of a multiporphyrinic rotaxane, Sauvage
and co-workers triggered the rotation of the ring around the
axle (Scheme 91).457 The [2]rotaxane 264 incorporated a
gold(III) porphyrin on the ring and two zinc(II) porphyrins on
the axle. Upon demetalation of Cu(I), which facilitated the
formation of the [2]rotaxane as a template, free rotation of the
wheel occurred. The extremely dierent and complementary
electronic properties of the gold(III) porphyrin (electron
acceptor) and zinc(II) porphyrin (electron donor) resulted in
attraction of three porphyrin parts and the rearrangement of
their positions from opposition to the same orientation.
Still on the basis of the transition-metal-containing rotaxane
system, Sauvage and co-workers rotated the ring around the
threaded dumbbell by electrochemical stimuli.458,459 In their
work, both 2,9-diphenyl-1,10-phenanthroline and 2,2:6,2-
with a binding constant of 2.3 105 M1 in water. CB[8]

resided at the central alkyl chain site of the guest. Upon
reduction, the terminal paraquat motifs became radical cation
units, which rapidly underwent an intramolecular pairing
process inside CB[8]. Accompanying this process, the shape
of the guest changed from linear to loop. As well as the shape,
its size was also changed substantially: the molecular dimension
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Scheme 90. A Lockable [1]Pseudorotaxane-Type Molecular Motor and Its Threading/Dethreading Movement
Scheme 91. Rotation of the Ring around the Axle by

MetallationDemetallation of the Central Coordination Site
Figure 22. Two types of molecular mobilities of rotaxanes: (a)

rotation and (b) shuttling.
terpyridine units were involved in the wheel-like component,

and the molecular string contained only one 2,9-diphenyl-1,10phenanthroline unit (see [2]rotaxane 266 in Scheme 92).
Varying the redox state of the copper (from CuI to CuII) led to
a large rearrangement of the surrounding ligands: CuI favored
two phenanthroline ligands, and CuII favored a phenanthroline
ligand and a terpyridine ligand. This relaxation process of the
compound induced pirouetting of the wheel around its axle,
which brought the system to its new equilibrium position. The
electrochemically induced motion was detected by cyclic
voltammetry. Further investigation on the chemical structural
inuence of the rotational movement indicated that, by using
long and exible linkers between the stoppers and the central
complex, ligand exchange was very fast, which led to short
response times (on the millisecond time scale and below).460
Alternating-current (ac) electric elds are commonly used to
interact with large-scale molecular motions, such as the
backbone uctuations of semirigid polymers.461 In 2000,
Leigh, Zerbetto, and co-workers used it to address the rotation
of the wheels of two hydrogen-bond-assembled rotaxanes
around their axles.462 It is an original application for ac electric
elds to probe the structures of rotaxanes. The chemical
structures of the threads were dierent in [2]rotaxanes 144a
and 146a, which aorded them dierent mobility properties
(Figure 23). Addressed by oscillating electric elds, [2]rotaxane
146a showed only rotary motion, while the other interlocked
molecule 144a displayed a more complex picture with a
superposition of rotation and pivoting motions. This

phenomenon could also be caused by thermal stimulus as
revealed by variable-temperature 1H NMR experiments.
The isomerization of an olen by light was used to trigger the
rotation of a ring along an axle.463 Because of the inuence of
an alternating-current electric eld, the rate of rotation of the
above-mentioned rotaxanes was slowed by 23 orders of
magnitude. To accelerate the rate of rotation, another broadly
useful stimulus, light, was used for the olen-based rotaxane
267 (Scheme 93). The two hydrogen-bond-accepting groups of
the trans-olen component were highly complementary to the
hydrogen-bond-donating sites of the tetralactam macrocycle.
Isomerization of the olen from trans to cis by light inevitably
disrupted the near-ideal hydrogen-bonding motif between the
macrocycle and thread and therefore dramatically reduced the
energy barrier for the macrocycle to pirouette around the axle.
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Scheme 92. Principle of the Electrochemically Induced Molecular Motions in a Copper Complex Rotaxane 266
Strategies for controlling rotational motion of rotaxanes have

been also devised by linking the rotor to the axle, to produce
new [1]rotaxanes.467 Rotaxanes 268271 that have been
designed for this investigation incorporated an -CD as the
rotor, a stilbene as the axle, and trinitrophenyl substituents as
the capping groups (Figure 24). It was indicated by 2D NMR
techniques that the -CD ring of rotaxane 269 without any
functional groups rotated freely around the stilbene axle;
incorporation of a methoxyl group into the axle, and the
succinamide link between the axle and -CD produced
rotaxane 268, which behaved analogously to a ratchet tooth
and pawl, respectively. The [1]rotaxane structure restricted the
rotational motion on the NMR time-scale. Alone, the eect of
the succinamide link of 271 was much less, and the methoxyl
group of 270 had no detectable eect.
Figure 23. Alternating-current electric eld-induced rotational motion

of rotaxanes 146a and 144a.
Thus, the rate of rotation of [2]rotaxanes was accelerated by >6

orders of magnitude.
Rotaxanes rotary property can also be altered by adding new
recognition sites to the interlocked molecules.464466 A
[2]rotaxane with a crown ether-containing wheel component
was investigated by Smith and co-workers. It showed the
capability to bind K+, which froze out a single coconformation
and therefore decreased the rotation of the wheel component.464 Furthermore, the inuence of anion and salt binding
properties and solvation of coconformations were evaluated in
detail.465,466
4.2.1. Observation of Shuttling and Its Dynamic

Control. The shuttling movement of rotaxanes was early
observed in 1991 by Stoddart and co-workers. The [2]rotaxane
1264PF6 consisted of a tetracationic cyclophane and a
polyether thread (Figure 25).294 The dumbbell-like molecule
contains two hydroquinol units, which provide two identical
stations for the wheel component. Hence, the tetracationic
macrocycle shuttled back and forth between the hydroquinol
Scheme 93. Rotational Motion of the Ring of Rotaxane 267 Accelerated by Light
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ring units, and the Gc value of ca. 13 kcal mol1 was

calculated from 1H NMR spectroscopy.
A similar translocation of macrocycles between two identical
stations in the threads was also achieved with the peptide
rotaxane systems driven by hydrogen-bonding interactions in
halogenated solvents.317,468 When the solvent was changed to
methanol, which reduced the strength of hydrogen bonding
and thus decreased the Gshuttling, the shuttling rate of the
macrocycle between the two peptide stations increased.
However, when DMSO was used as the solvent, the macrocycle
in [2]rotaxane 272 stopped shuttling and stayed on the
lipophilic station due to lack of hydrogen bonding (Scheme
94a). Besides the solvent inuence, other factors controlling the
rate of shuttling were also investigated. Decreasing the
temperature and adding steric barriers between the two stations
in the threading molecules both freeze the shuttling macrocycle
at a single peptide station. For example, the shuttling in the
sulfur-linked rotaxane 273 was suppressed by introduction of a
bulky tosyl imino group (TsNCl, Bu4NOH, CH2Cl2, 2 h, 93%)
to the thread. Reduction (P4S10, CH2Cl2, 4 h, 100%) of the
imine re-established the shuttling motion (Scheme 94b). The
strategy of adding steric barriers to hinder the shuttling
movements was also adopted by Stoddart and co-workers in a
[2]rotaxane containing DB24C8 and a dumbbell with two
dialkylammonium recognition sites.469
To achieve reversibility of controlling the shuttling movement on and o, several methods based on noncovalent
interactions or external stimuli are tried and show very good
results. For example, alternating intermolecular complexation
and decomplexation processes are involved in the linker unit,
which connects the two shuttling stations on the dumbbell
component.470 [2]Rotaxane 275 was based on the recognition
of the bipyridinium unit with BPP34C10 (Scheme 95). The
linker between the two equivalent stations contained a
Figure 24. Schematic representation of a tooth and pawl restricting

rotational motion in -CD-based rotaxanes. Reproduced with
permission from ref 467. Copyright 2003 Wiley-VCH Verlag GmbH
& Co. KGaA, Weinheim.
Figure 25. Molecular shuttle 126 with two identical stations.

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Scheme 94. Peptide-Based Molecular Shuttles and Their Dynamic Control by (a) Solvents and (b) Steric Barriers
Scheme 95. Intermittent Molecular Shuttle as a Binary Switch
motions in [2]rotaxanes.471 Furthermore, photochemical

stimuli can be used as a brake for rotaxane-based shuttles.472
Recently, a light-gated STOP-GO molecular shuttle was
designed and constructed on the basis of a bistable rotaxane
linked by tetrauoro-4,4-azobiphenyloxy units (Figure 26).
When the rotaxane was in its trans conguration, the blue box
moved back and forth between the two DNP units at 309 K.
Furthermore, the photoisomerization of trans-2764PF6 to cis-
bipyridine moiety, which acted as a ligand for coordination with

CuI ion. When these chelating sites combined with CuI ion, the
shuttling of the macrocycle was hampered. However, treatment
of the complex with a suspension of ion-exchange resin led to
the complete decomplexation, and the shuttling of the
macrocycle happened again. It acted as a molecular switch to
dominate the dynamic state of the rotaxane-based shuttle.
Besides the coordination interaction involved above, electrostatic interactions have also been used to switch the shuttling
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Figure 26. A light-gated STOP-GO molecular shuttle based on [2]rotaxane 2764PF6. Reproduced with permission from ref 472. Copyright 2009
Scheme 96. Conformational Isomerism of the Peptide in [2]Rotaxane 277
external stimuli to become the latter preferential binding site of

the macrocycle.
4.2.2.1. Chemical Stimuli. Shuttling motions of the
macrocycles in rotaxanes can be triggered by addition of
chemical reagents. In some cases, through changing solvents,
the localization of macrocycles can be altered.473,474 The
polarity of solvents can be a factor controlling the shuttling
movement. One such example involved an environmentally
sensitive peptide [2]rotaxane reported by Leigh and coworkers.474 The [2]rotaxane 277 containing sarcosylglycine
unit exhibited only the E tertiary amide rotamer in apolar
solvents, as the Z rotamer allowed the formation of two
2764PF6 stopped the shuttling motion. This work provides a

useful method to control molecular shuttles at will.
4.2.2. Stimuli-Responsive Molecular Shuttles. When
the shuttling motion was observed in rotaxane systems,
chemists began to modulate the shuttling speed from fast to
slow mode or from on to o via various routes. After that,
eorts were made to reversibly control the shuttling movements from one station to another under external stimuli, such
as chemical, photochemical, and electrochemical stimuli. In this
regard, the two recognition sites in the dumbbell components
are always dierent from each other, one of which is the initially
favored position for the wheel, and the other can be altered by
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Scheme 97. Protonation or Electrochemical Oxidation of the Benzidine Station in the Axle Resulting in Shuttling Motion of the
Bead
Scheme 98. An AcidBase Controlled Molecular Shuttle
favorable hydrogen bonds as compared to four in the E

rotamer. In hydrogen-bond-competing solvents, such as
DMSO-d6, hydrogen-bonding interactions between the peptide
and macrocycle were broken, and the macrocycle preferred to
be positioned over the C-terminus amino acid of the thread,
which resulted in a mixture of two rotamers (Scheme 96).
The most common situation for chemical stimuli is pHcontrol of shuttling movement.475 An early example for
controlling the position of the macrocycle at one station or
another through addition of acid or base was reported by Kaifer
and co-workers in 1994.476 The [2]rotaxane 2784PF6 that they
chose for investigation contained the CBPQT4+ macrocycle and
a linear molecule with benzidine and biphenol units. At 229 K,
the macrocycle mainly occupied the benzidine position in the
dumbbell, because the binding anity of CBPQT4+ for the
benzidine derivative was about 10 times greater than that for

the corresponding biphenol derivative. Addition of excess TFA
to the system resulted in macrocyclic translation to the
biphenol station (Scheme 97). Subsequently reversible
behavior could be obtained by neutralization of TFA with
pyridine. Another important feature of this rotaxane-based
shuttle was that it could also be triggered by electrochemical
means as analyzed by UVvis spectroscopy and cyclic
voltammetry.
It is well-known that pseudorotaxanes containing ammonium
ions are often triggered by addition of acidbase pairs to
achieve their association/dissociation movements. On the basis
of the formation of pseudorotaxane-type inclusion complexes
between secondary dialkylammonium ions (NH2+) or paraquat
and DB24C8, a bistable rotaxane 2793PF6 was described with
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Scheme 99. A pH-Switchable Molecular Shuttle through Anion Recognition
Scheme 100. A pH-Switchable Palladium-Complexed Molecular Shuttle
a dumbbell-shaped component possessing both NH2+ and

N,N-dialkylated-4,4-bipyridinium (Bpym2+) units (Scheme
98).477 The rings position between the two dierent
recognition sites was switched by pH stimuli. Deprotonation
of the NH2+ center was expected to induce the displacement of
the ring to the Bpym2+ station. Because the Bpym2+ unit was
very sensitive to nucleophilic bases, it was not easy to choose an
appropriate base. Diisopropylethylamine (i-Pr2NEt) and
tributylamine (Bu3N) were at last found to be ideal bases.
Reprotonation could be performed by the addition of TFA or
triic acid. To easily monitor the systems state, an anthracene
moiety was chosen as a stopper due to its absorption,
luminescence, and redox properties. According to recent

research, the following investigation on the binding abilities
of various interaction sites for DB24C8 were carried out.478
The results indicated that the anity of dierent stations for
DB24C8 at room temperature was determined as follows:
anilinium > monosubstituted pyridinium amide triazolium >
disubstituted pyridinium amide > aniline.
In another mechanism for molecular shuttles based on the
change of pH strategy, the hydrogen-bonding stations for the
macrocycle can be altered by anion formation.479 [2]Rotaxane
280 contained a thread that featured two potential hydrogenbonding stations (the succinamide group and cinnamate group)
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Scheme 101. Shuttling Motion of the Macrocycle through the Alternative Addition of Li+ and 12C4
Scheme 102. Shuttling Motion of [2]Rotaxane 283 through the Stepwise Competitive Binding of Transition-Metal Ions
Bu4NOH, t-BuOK, DBU, and phosphazine P1, the translocation of the macrocycle in the phenolate anion station was
displayed. The shuttling was reversible after addition of
CF3CO2H, which returned the macrocycle to the original
for the benzylic amide macrocycle (Scheme 99). In the neutral

form, the macrocycle resided preferentially on the succinamide
station, while after addition of bases that were capable of
deprotonating the phenol, such as LiOH, NaOH, KOH, CsOH,
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Scheme 103. An Allosterically Regulated Molecular Shuttle
Scheme 104. Shuttling through Reversible Covalent Bond Formation
shuttle.480 During the shuttling process, a palladium-complexed

macrocycle was translocated between 4,4-dimethylaminopyridine and pyridine monodentate ligand sites triggered by adding
or removing TsOH (Scheme 100). In other words, protonation
of the more basic heterocycle determined the position of
equilibrium because the NH bond is signicantly stronger
than the PdN bond. This metalligand coordination driven
(and dynamic covalent chemistry) molecular shuttle could play
a prominent role in the construction of articial molecular
machines.
Besides the pH stimulus, some other chemical reagents such
as cationic compounds76,481,482 or halogen and acetate
anions483 have also been used to shuttle the macrocycles in
rotaxanes. For example, Sanders, Stoddart, and co-workers
developed a Li+-driven molecular shuttle based on a [2]rotaxane with DNP38C10 as the ring component and an axle
succinamide station. The anion-induced shuttling has several

remarkable features. First, it is highly solvent dependent.
Solvents like DMF, CH3CN, and CH3OH, in which the
designed hydrogen-bonding interactions are relatively weak, are
chosen for this system. Second, although the nature of the
accompanying cation strongly inuences the strength of anion
hydrogen bonding, the counterion does not aect the
coconformation adopted by anion in the rotaxane. Third, the
presence of alternative anionic hydrogen-bond acceptors, such
as Bu4NX (X = F, Cl, Br, I, HO, NO3, AcO), does not
aect the shuttling process either.
On the basis of acidbase stimuli, the pyridine motifs on
threads could be protonated and decomplexed from metal ions
to trigger the shuttling motion of coordination-derived
rotaxanes. Inspired by this mechanism, Leigh and co-workers
reported a pH-switchable palladium-complexed molecular
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Scheme 105. A Fluorescence Switch That Can Be Independently Operated by Both Acid/Base and Metal-Ion Complexation/
Decomplexationa
Reproduced with permission from ref 333. Copyright 2012 John Wiley & Sons, Ltd.
Scheme 106. Photoinduced Molecular Shuttle of Rotaxane 288 through E/Z Photoisomerization of the Azobenzene Dumbbell
acetone at 298 K. After addition of CuII or CdII ions, although

the terminal peptide carbonyl group chelated to the metal, the
preferred position of the macrocycle remained unchanged.
Translocation of the macrocycle to the succinic amide ester
station was caused by subsequent deprotonation of the amide
proton of the coordination part with phosphazene base P1-tBu.
The stepwise shuttling process was fully reversible with the
addition of NaCN to remove the metal ion and NH4Cl for
reprotonation of the amide nitrogen atom.
In the following example, the shuttle motion was also
stimulated by adding the CdII ion, but the mechanism was
completely dierent.482 When the bis(2-picolyl)amine (BPA)
moiety was attached directly to the succinamide unit, which was
considered as one hydrogen-bonding station of the thread,
chelation of a metal ion used all three nitrogen atoms of the
containing a naphthaldiimide station and a pyromellitic diimide

station (Scheme 101).76 The macrocycle initially resided on the
naphthaldiimide station due to the better -stacking interactions. Because two Li+ ions form a strong 2:1 complex with
DNP38C10 and pyromellitic diimide station, the position of
the macrocycle was changed. Subsequent addition of 12-crown4 (12C4) induced the reverse process as 12C4 was a very
strong sequestering agent for Li+.
Transition-metal ions such as CuII or CdII have also been
involved in switching the position of macrocycles on
threads.481,482 [2]Rotaxane 283 had a glycylglycine station, as
well as the succinic amide ester station on the thread for
binding the benzylic amide macrocycle (Scheme 102).481
Without metal ions, the occupancy of the macrocycle was
approximately 90:10 in favor of the glycylglycine station in
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Scheme 107. Unidirectional Photoinduced Shuttling in [2]Rotaxane 289 with a Symmetric Stilbene Dumbbell
Scheme 108. A Lockable Light-Driven Molecular Shuttle with a Fluorescent Signal
an amide unit. The molecular switch can be operated by

changing pH or by adding or removing Li+ or Zn2+.
Signicantly, the three independent movement processes
were all accompanied by multilevel expression of uorescence.
4.2.2.2. Photochemical Stimuli. Light-driven molecular
shuttles are of considerable interest because their response to
a photochemical process is usually rapid and precise and can be
operated remotely without generating any chemical waste. In
1997, Nakashima and co-workers reported an example of a
light-driven rotaxane-based molecular shuttle.486 At room
temperature, the -CD macrocycle stayed at the azobenzene
moiety. After UV irradiation, the wheel moved to the
methylene spacer caused by the photoisomerization of the
azobenzene unit from the trans to the cis conguration (Scheme
106). Moreover, irradiation with visible light resulted in the
reverse process. It is indicated that E/Z photoisomerization of
the azobenzene dumbbells is an ecient method to achieve
light-driven translational motion in molecular shuttles.487
Stilbene is a molecule similar to azobenzene and can also be
switched between its cis and trans conformations by light. There
is an interesting feature when a symmetric stilbene component
is chosen as a dumbbell and nonsymmetric CD molecule is
chosen as a wheel.488 The unidirectional photoinduced
shuttling in such a rotaxane was unprecedented with the cis
alkene unit near the narrow rim of -CD (Scheme 107). The -
BPA group, which caused the pyridine arms to twist

orthogonally and enter the space that was already occupied
by the benzylamide macrocycle (Scheme 103). Therefore, the
conformational change led to translocation of the macrocycle to
the inherently weaker hydrogen-bonding succinic amide ester
site 1.5 nm away. Addition of NaCN led to removal of Cd2+
and repositioning of the macrocycle. This was a negative
heterotropic allosteric binding event, which provided a new
strategy for metal-binding events to construct functional
molecular machines.
A bistable stimuli-responsive molecular shuttle can also be
triggered through the formation (and breaking) of CC bonds,
using the well-established DielsAlder and retro-DielsAlder
reactions.484 Rotaxane 285 contained a trans double bond
holding the two amide carbonyls of the fumaramide station
complexed with the benzylic amide macrocycle, which also
opened the possibility of utilizing reversible CC bond
formation to trigger the shuttling response (Scheme 104). It
provided a new way to switch the position of the macrocycles.
Recently, an interesting molecular shuttle was reported,
which could be independently operated by both acid/base and
metal-ion complexation/decomplexation (Scheme 105).485 In
this report, an appropriately designed crown ether-based
macrocycle was bound mechanically onto a dumbbell
possessing two dierent recognition sites, a NH2+ center and
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Scheme 109. A Photoresponsive H-Bond-Assembled Molecular Shuttle
Scheme 110. Chemical Structure of [2]Rotaxane 292 and the Proposed Mechanism for Its Excited-State Dynamicsa
CD ring resided on the stilbene unit initially and slid to the

biphenyl unit under the irradiation at 340 nm. The reverse
process could be realized by the irradiation at 265 nm, making
the -CD ring reside on the stilbene unit again.
The usual methods used to monitor the position change of
macrocycles in rotaxanes are based on 1H NMR, absorption,
and circular dichroism spectroscopies. Changes in uorescence
are easily detected output signals for shuttling motion. One
interesting example was demonstrated by Tian and coworkers.489,490 In the initial work, the strong hydrogen-bonding
interaction between the -CD macrocycle and the isophthalic
acid unit prevented the shuttling motion of the ring along the
two binding sites even if the system was irradiated by light and
the trans-stilbene changed to the cis-stilbene (Scheme 108).489
By the addition of a base such as Na2CO3, the hydrogen bonds
were destroyed. Thus, the -CD macrocycle could shuttle back
and forth upon the E/Z photoisomerization of stilbene. The
motional process was operated by alternating the irradiation
frequency, which was accompanied by obvious changes in the
intensity of uorescence at 530 nm. This switching system
featured the convenient use of an optical input and easy reading
of the optical output. Later, a novel light-driven [3]rotaxane
molecular shuttle was synthesized and characterized, in which
the two -CD rings shuttled back and forth on the molecular
thread that contained an azobenzene unit, a biphenyl unit, and

a stilbene unit.491
Besides azobenzene and stilbene moieties, spiropyran is also
a typical photoisomerizable compound, which can be exploited
for the construction of rotaxane-based shuttles.492 On all
accounts, due to the remarkable dierence of the two
photoisomers and their high reversibility under irradiation,
the photoisomerization strategy has been widely applied for the
fabrication of various optical molecular shuttles. In other cases,
photoinduced chemical reaction493 and photoinduced electrontransfer494 have also been included to drive molecular shuttles.
For example, aryl cycloheptatrienes, which can be photochemically converted into the related tropylium ions, have been used
to monitor the coconformational change of rotaxanes as one
station of the linear component.493
A photosensitizer such as naphthalimide can be designed as
one binding site for the macrocycle in a bistable rotaxane.494 In
2001, Leigh and co-workers reported photoinduction of fast,
reversible translational motion in a molecular shuttle based on a
peptide [2]rotaxane with two binding sites, a succinamide unit
and a naphthalene imide unit (Scheme 109). In the general
state, the succinamide site was an excellent t for the benzylic
amide macrocycle as compared to the naphthalimide unit,
which was a poor H-bond acceptor. After photoreduction by an
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Scheme 111. Chemical Structure and Shuttling Principle of Coordination [2]Rotaxane 293
second time scale.495 The supramolecular system consisted of a

tetralactam macrocycle and a dumbbell-like component
containing a glycylglycine recognition unit and a bulky
anthracene stopper (Scheme 110). It was conrmed by 1H
NMR spectroscopy and X-ray crystallography that rotaxane 292
adopted coconformations with the macrocycle surrounding the
peptide part of the thread in relatively nonpolar solvents. After
optical excitation, the macrocycle was displaced from the
peptide station to the carbonyl unit directly attached to the
anthracene. The explanation was given that in the excited
singlet state, hydrogen bonding between the macrocycle and
the carbonyl group was enhanced through a considerable
transfer of charge from the anthracene ring onto the carbonyl
oxygen atom. It provided a new principle for macrocycle
motion in molecular shuttles.
4.2.2.3. Electrochemical Stimuli. Electrochemistry is an
attractive method to trigger the shuttling behavior of rotaxanes
because it can be easily and rapidly turned on and o. What is
more, it is also a reagent- and waste-free procedure. Another
external donor such as 1,4-diazabicyclo[2.2.2]octane (DABCO)

and a nanosecond laser pulse, naphthalimide became a radical
anion, which greatly enhanced its H-bond-accepting anity and
therefore made it bind strongly to the wheel. The wheel was
driven from the original succinamide station to the naphthalene
imide station. This process was determined by transient
changes in the optical absorption spectrum after photoexcitation. Furthermore, the macrocycle moved back to its
original position after charge recombination to make the
process reversible and cyclable. This molecular shuttle may be
applied in the fetching-and-carrying of molecules or clusters
of atoms between specic locations such as across membranes
or the construction of photoresponsive molecular devices.
Controlling shuttling motions of the above-mentioned
photoactive rotaxanes requires external reagents such as
sacricial reductants and photosensitizers to be added. There
also exists an unexpected photoinduced coconformational
change based on a rearrangement in the pattern of hydrogen
bonds between the thread and macrocycle. No external
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Scheme 112. Shuttling Movement of CBPQT4+ between the TTF and DNP Recognition Units in [2]Rotaxane 2944PF6
Scheme 113. An Electrochemically Driven Molecular Switch Based on [2]Rotaxane 2954PF6 with a Rigid Axle
stay in the recognition site with bidentate chelation. Upon

oxidation by electrochemical process, the system was switched
from four-coordinate to ve-coordinate and the process was
reversible. As compared to the similar catenane species,499 the
metal ion in the rotaxane was less protected from interaction
with external species. Furthermore, an oxidative photochemical
process could also be used as a stimulus for the motion.
TTF is an excellent component for the construction of
redox-driven molecular switches because it forms a strong
green-color 1:1 complex (Ka = 8000 M1 in MeCN) with
CBPQT4+ and is easily oxidized to TTF+ and TTF2+ ions.428 It
advantage is that the same stimulus can simultaneously act as

both eector and detector of the motion.496
The motions of coordination supramolecular systems
developed by Sauvage and co-workers were mostly driven by
electrochemical signals.497 The general principle is based on
two markedly dierent coordination environments for the CuI
and CuII ions. Such an electrochemically controlled rotaxanebased molecular shuttle was designed and operated successfully
in 1999; it consisted of both a coordinating ring and a
molecular thread containing two dierent coordination sites
(Scheme 111).498 The stable CuI complex made the macrocycle
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Scheme 114. Assembly of an Electrochemically Driven Molecular Shuttle on an Au Surfacea
was characterized by chronoamperometric and impedance

measurements. It was also demonstrated that electrochemical
shuttling of the redox-active cyclophane around the molecular
string controlled the hydrophobic/hydrophilic properties of the
interface, implying that directional molecular mechanical
motion in supramolecular systems might be translated into
controlled motion of bulk liquids in appropriate surfacemodied containers.
Electrochemical stimuli can have a dramatic eect on
hydrogen-bonding interactions. On the basis of this mechanism, Leigh and co-workers reported a series of electrochemically switchable hydrogen-bonded molecular shuttles containing succinamide and naphthalimide hydrogen-bonding stations
for a benzylic amide macrocycle.504 The ring initially resided on
the succindiamide moiety due to the favorable hydrogenbonding interactions (Scheme 115). By reduction of the
has been used as one of the binding stations on dumbbells for

the construction of molecular shuttles. In the initial research, a
monopyrrolotetrathiafulvalene (MPTTF) moiety was chosen
to bind CBPQT4+ in competition with a 1,5-dioxynaphthalene
(DNP) unit.297 Unfortunately, there simultaneously existed two
stable translational isomers in a 1:1 ratio in acetone at room
temperature. To improve the situation, MPTTF unit was
replaced by a disubstituted TTF.500 It was revealed by UV/vis
spectroscopy that the TTF site was rst encircled by the
CBPQT4+ ring. Addition of Fe(ClO4)3 as an oxidant led to the
formation of the TTF+ radical cation and the TTF2+ ion,
which produced a chargecharge repulsion between the
oxidized TTF+/2+ unit and the CBPQT4+ ring and resulted
in the movement of the ring from the TTF unit to the DNP
moiety (Scheme 112).501 The reverse process was achieved by
the addition of Zn powder as characterized by UV/vis and 1H
NMR spectroscopies. During the process, the CBPQT4+
component moved 3.7 nm between the TTF and DNP
recognition sites.
In the above research, the use of the TTF unit in the
dumbbell component led to the problem that the dumbbell
existed as two inseparable isomers created by the facile cis/trans
isomerization of TTF. Replacing the TTF unit by the isomerfree MPTTF overcame this shortcoming. However, most
investigated MPTTF-containing two-station [2]rotaxanes were
mixtures of two possible translational isomers in which the
CBPQT4+ ring encircled two units equally. Further research
involved the incorporation of a rigid spacer into the two-station
[2]rotaxane 2954PF6, which resulted in a very favorable and
temperature-independent isomeric distribution of the rotaxane
with the macrocycle staying at the MPTTF site (Scheme
113).502 An eletrochemical stimulus was used to trigger the
shuttling motion reversibly. It was calculated from CV that the
switching distance was 1.5 nm between the two states. This
strategy provided a new concept that utilization of rigidity
could be better to obtain well-dened structures and functions
in the fabrication of molecular pistons and simple motor
molecules.
Not only can the binding station on the thread be triggered
by electrochemical signals, but the macrocycle such as the
tetracationic cyclophane can also be induced by the reduction
or oxidation process, and subsequently move back and forth
between the two stations on the string.427 Willner and coworkers developed a redox-active [2]rotaxane 296 as a
monolayer assembly on an Au electrode.503 The [2]rotaxane
comprised a CBPQT4+ cyclophane threaded onto a molecular
string that included a -donor diiminobenzene unit and an
adamantine stopper (Scheme 114). The cyclophane initially
localized on the diiminobenzene unit, and the shuttle was
induced by the reduction or oxidation of the cyclophane, which
Scheme 115. An Electrochemically Switchable, HydrogenBonded Molecular Shuttle
naphthalimide moiety to the corresponding radical anion, the

macrocycle-binding ability of the two binding sites was altered
by over 8 orders of magnitude, which induced the shuttling
motion. The reverse process was realized by the oxidation of
the naphthalimide radical anion. As described in Scheme 109,
the shuttling motion could be induced both by electrochemical
stimuli and by photochemical stimuli.
To investigate the shuttling characteristics of the above
shuttle comprehensively, the naphthalimide unit on the thread
was replaced by a naphthalene-1,4,5,8-diimide.505 As compared
to the single imide group, the more extensively delocalized
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Scheme 116. Three-State Redox-Active Molecular Shuttle 297
Scheme 117. Entropy-Driven Tristable Molecular Shuttle 298a
(a) h (254 nm), 20 min, CH2Cl2, 298 K, 54%, or h (350 nm), catalytic benzophenone, 5 min, 65%; (b) h (312 nm), 35 min, CH2Cl2, 298 K,
>95%, or h (400670 nm), catalytic Br2, 2 min, CH2Cl2, 298 K, 100%; (c) CDCl3, 258 K, 85%; (d) CDCl3, 308 K, 90%; (e) h (312 nm), 35
min, CH2Cl2, >95%, or h (400670 nm), catalytic Br2, 2 min, CH2Cl2, 100%; (f) h (254 nm), 20 min, CDCl3, 258 K, 54%.
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Scheme 118. A Multi-Stimuli-Driven Molecular Shuttle 299
part, we will mainly focus on the cooperative eects of dierent

driving forces.
Leigh, Zerbetto, and co-workers reported a light- and
entropy-driven tristable molecular shuttle, in which the ring
could be switched among three dierent positions on a thread
(Scheme 117).506 The [2]rotaxane 298 consisted of the
benzylic amide macrocycle with endo-pyridine units, and a
thread containing a fumaramide group and a succinic amide
ester unit separated by a dodecane chain. Without any stimuli,
the position of the macrocycle was over the fumaramide station
at room temperature. Photoisomerization of stilbene on
irradiation with 254 nm light aorded the cis-[2]rotaxane,
which led to displacement of the macrocycle to the succinic
amide ester site on the thread at room temperature. However,
the conformation of the cis-rotaxane was highly temperature
dependent. At 258 K, the macrocycle was not primarily located
over either of the designed stations, but positioned over the
alkyl chain. To satisfy the hydrogen-bonding requirements of
the macrocycle, the alkyl chain presumably adopts a folded Sshape conformation. It provided a useful means of controlling
translational isomerism in a rotaxane by varying the temperature.
Nakashima and co-workers developed a multi-stimuli-driven
molecular shuttle, which contained -CD as the ring,
azobenzene as the photoactive group, paraquat as the energy
barrier for slipping of the ring, and 2,4-dinitrobenzene groups
as the stoppers (Scheme 118).507 The [2]rotaxane 299 showed
aromatic system had a less negative reduction potential for the

formation of the radical anion, but also exhibited a second
reduction process to give the dianionic state. Therefore, a threestate redox-active molecular shuttle was designed and
synthesized (Scheme 116). The reversible and cyclable
switching process was conrmed by cyclic voltammetry. The
translational isomer ratios and shuttling dynamics for their
interconversion in each state were also quantied. The
reduction potential of the naphthalene diimide unit was
suciently low (0.68 V) to make the rotaxane compatible
with operation in self-assembled monolayers on gold. This is
the rst time that the electrochemically induced shuttling
between two states has been demonstrated for a self-assembled
monolayer of amide-based molecular shuttles. It provides a
signicant new platform to achieve molecular machines on
surfaces.
4.2.2.4. Multiple Stimuli. As described above, most external
stimuli used to induce shuttling are based on the addition of
chemical reagents, light, and electrochemistry. A simple
temperature or solvent change can also reverse the relative
binding anity of the macrocycle for dierent stations. In some
cases, particularly in complicated systems, molecular machines
are triggered by cooperative eects of multiple stimuli to
generate some specic functions.506508 Some examples such as
a pH-driven molecular shuttle triggered by redox stimulus476 as
demonstrated before can be included in this category. In this
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a reversible isomerization between the trans- and cis-forms of

the azobenzene moiety via irradiation with UV light and visible
light alternatively, and shuttled back and forth between the
azobenzene and the alkylene moieties. Interestingly, the
shuttling motion happened only in DMSO, but not in water.
Furthermore, it was conrmed by the dynamic NMR, NOE
dierential, and CD spectroscopies that during the shuttling
process in DMSO, the -CD ring moved to the azobenzene
moiety at temperatures below 100 C, while after the
temperatures reached above 100 C, it was displaced between
the azobenzene moiety and the propylene moieties. Thus, the
shuttling distance could be controlled by temperature. This
system achieved the shuttling movement driven by light,
heating, and solvent polarity, respectively, and provided the
opportunity to design and develop nanoscale switching devices
based on multi-stimuli-driven molecular shuttles.
4.2.3. Modulating Properties and Functions of
Molecular Shuttles. 4.2.3.1. New Features of Molecular
Shuttles. Studies on switching the positions of macrocycles in
bistable rotaxane-based molecular shuttles have developed
rapidly and widely. Chemists have started to pay attention to
the functions of the molecular shuttles. In 2002, Leigh,
Zerbetto, and co-workers reported a system in which a
translational movement of a tetralactam macrocycle along a
chiral peptide thread elicited a chiral optical response driven by
the polarity of the solvent.509 It was initially indicated that the
chirality of the molecule could be switched on and o by
controlling the interactions between mechanically interlocked
submolecular components as evidenced by circular dichroism
(CD). Subsequently, the same group found another method
through photochemical stimuli to construct chiroptical switching in a bistable molecular shuttle (Scheme 119).510 In this
system, glycyl-L-leucine with an asymmetric center acted as one
binding site on the axle for the wheel-like component. Upon

photoisomerization of the olen station on the thread, the ring
moved to the glycyl- L -leucine unit from its previous
fumaramide portion. The process provided a chiral optical
response from the chiral station as evidenced by CD
spectroscopy.
In a hydrogen-bond-assembled fullerene molecular shuttle,
the dierent locations of the macrocycle were achieved by
changing solvent from dichloromethane to dimethyl sulfoxide,
which led to the macrocycle being close to the fullerene
spheroid or far away (Scheme 120).511 Although the proximity
Scheme 120. Hydrogen-Bond-Assembled Fullerene
Molecular Shuttle 301
Scheme 119. Switching On and O the Expression of

Chirality in Peptide Rotaxane 300a
of the macrocycle did not aect the uorescence, a signicant

eect on the triplettriplet spectrum of the fullerene fragment
was detected by 1H NMR and time-resolved spectroscopy. In
another example reported by Li and co-workers, the macrocycle
translocation switched the energy transfer from the pyrene unit
to the perylene moiety, which elicited a uorescence
response.512
4.2.3.2. Construction of Molecular Machines. Stimuliresponsive molecular shuttles provide a promising basis for
articial molecular machines. Various types of rotaxane
structures provide good platforms to construct molecular
machines, such as molecular logic gates, switches, necklaces,
nanomotors, elevators, or molecular rachets. Several typical
examples of the functional molecules will be described in this
part.
Supramolecular systems can be used to construct molecular
logic gates to exploit the abilities of molecules to process
information. A half adder, with distinct AND and XOR logic
gates, was reported on the basis of a [2]rotaxane system 302
that was driven by photochemical stimuli and gave rise to
optical outputs (Scheme 121).513 The [2]rotaxane was
comprised of an -CD macrocycle locked onto a dumbbell
with two dierent photoswitchable binding sites, an azobenzene
(a) Either 254 nm, CH2Cl2, 20 min, 56%, or 254 nm, CH3CN, 20
min, 49%, or 350 nm, benzophenone, CH2Cl2, 20 min, 70%; (b) either
312 nm, CH2Cl2 or CH3CN, 20 min, 62%, or 400670 nm, cat. Br2,
CH2Cl2, 2 min, >95%, or 130 C, C2H2Cl4, 6 days, 95%.
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Scheme 121. A Half Adder Based on Rotaxane 302 Driven by Photochemical Stimuli
site and a stilbene site, and was end-capped by two uorescent

units, which could be switched independently by using light at
dierent wavelengths (UV/vis). The AND gate could be
realized by the output of the changes of absorption response to
the two dierent inputs (irradiated at 380 and 313 nm). The
XOR gate could be realized by the uorescence output in
response to the same inputs. Last, the two signals were
combined to construct a half adder, which is widely used in
mathematics and computing. It is worth mentioning that all of
the processes are reversible, indicating that the half adder can
be operated repeatedly. This is an early example to mimic a half
adder on a unimolecular scale, and gives us an idea to construct
more sophisticated systems that involve complicated logic
circuits. Molecular logic gates with superior processing
capabilities may be realized to break through the physical
limits of the silicon chips if the logic circuits can function in
solid-state molecular electronic devices.
Harada and co-workers reported a molecular abacus based on
a molecular necklace of -CD molecules threading onto
poly(ethylene glycol) chains.514 The selected -CD molecules
reversibly shuttled using a scanning tunneling microscope

(STM) under mild conditions in air at room temperature
(Figure 27). Three modes of transformation were manipulated
and observed by STM: shuttling of a single -CD ring,
simultaneous movement of a pair of -CDs, and a hook-shape
motion formed by the synchronized repositioning of several CDs. A more complicated system was developed by combining
the three modes of transformation. It represents a very
important stage in the development of molecular devices,
which are the ultimate devices in terms of large-scale
integration.
Another abacus-like machine was operated by light stimulus,
which contained BPP34C10 as a wheel, a dumbbell component
with two bipyridinium units, and a photoactive stopper.515
Stoddart and co-workers developed a linear autonomous
articial nanomotor powered by sunlight without generation
of waste products. The shuttling movement was undergone in
an intramolecular charge-separated state.31 As described in
Scheme 122, irradiation of the rutheniumtrisbipyridine
complex (green structure) generated a highly reduced excited
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cyclestation interactions so that the macrocycle preferred to

relocate to the alternative paraquat unit (pink). Remarkably, in
this system, the back electron-transfer process was slow enough
to allow shuttling of the ring toward the other station in
approximately 10% of the molecules in the relaxed process. The
system was remarkably stable under mild conditions, and could
be driven at high frequency (kilohertz).
Development of supramolecular architectures often goes
along from the simple to the complex. By combination of three
linear rotaxane-based shuttles, a nanometer-scale molecular
elevator was designed and successfully operated.32 This system
initially formed a pseudorotaxane-like complex 306305 that
had a tritopic host with three DB24C8 rings fused together by a
triphenylene core, and a trifurcated guest with three
dibenzylammonium ions and paraquat units linked to a central
benzenoid core (Scheme 123). By functionalization of the ends
of each leg of this pseudorotaxane with bulky 3,5-di-tertbutylbenzyl feet, the rotaxane-type elevator 307 formed and
was characterized by 1H NMR spectroscopy, electrochemistry,
and absorption and uorescence spectroscopy. It was circa (ca.)
2.5 nm in height with a diameter of ca. 3.5 nm, and the distance
traveled by the platform was about 0.7 nm. Because of the
acidbase switching ability of a [2]rotaxane based on the
DB24C8/secondary ammonium salt recognition motif,79 this
triply threaded two-component system translated up and down
on alternative addition of slightly more than 3 equiv of
appropriate acid and base. During the shuttling movement from
the upper to lower level, a force of up to 200 pN was generated.
Furthermore, from a plot of the absorbance changes on
titration of the system with base, it could be shown that there
existed three quite distinct steps and the recognition sites
operated not in unison but rather one after the other.
Figure 27. A molecular abacus through STM manipulation of a CD

necklace. (a) Chemical structure of the CD necklace; and (bd)
shuttle manipulation by STM. Reproduced with permission from ref
state. An intramolecular electron transfer then occurred

between the excited metal center and the most easily reduced
paraquat station (blue), on which the macrocycle resided
preferentially. The result was destabilization of the macro-
Scheme 122. A Linear Autonomous Articial Nanomotor 304 Powered by Sunlighta
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Scheme 123. (a) Synthesis of a Molecular Elevator and (b) Cartoon Representation of Operating It by Acid/Base Paira
co-worker, acted as a compartmentalized molecular machine

with the behavior of ratcheting a particle energetically uphill.33
Control over the kinetics for exchange of the substrate between
two sites of the machine was introduced to create articial
Brownian machines, which were more sophisticated than
simple positional switches. The rotaxane-based system 309
was initially statistically balanced. After being triggered by a
balance-breaking stimulus upon irradiation with 312 nm light to
generate a 49:51 2% E:Z photostationary state and followed
by removal of the kinetic barrier, the balance was restored by
biased Brownian motion of the ring toward the new equilibrium
distribution. When the barrier was restored, the system became
unlinked and was not in equilibrium, although statistically
balanced. The last resetting step through the Z/E olen
isomerization made the system statistically unbalanced,
unlinked, and not in equilibrium. This stimuli-induced
irreversible molecular machine in the position of the macrocycle represented a new type of molecular shuttle in
phenomenological terms.
Another way of amplifying and harnessing molecular

shuttling motions is the formation of linear articial molecular
muscles. One example was based on the switchable and bistable
[3]rotaxane 308 with a pair of mobile CBPQT4+ rings
encircling a single dumbbell containing TTF and NAP stations
(Scheme 124a).516 The locations of the two ring components
of this [3]rotaxane along its dumbbell-shaped component could
be controlled precisely either by chemical or by electrochemical
stimuli with the inter-ring distance changing from 4.2 to 1.4
nm. At low temperatures, it was revealed by fast scan-rate cyclic
voltammetry that the two rings of the [3]rotaxane moved
stepwise from their respective ends of the rotaxane under redox
conditions. Furthermore, disulde tethers attached covalently
to the rings were designed for the purpose of their self-assembly
onto a gold surface. Because of anchoring to a nanoelectromechanical system, the device underwent controllable
and reversible bending when subjected to chemical oxidants
and reductants (Scheme 124b). It was indicated by control
studies that the contraction and extension movements of the
surface-bound molecular muscles changed 5 orders of
magnitude in size. This observation gives evidence for the
hypothesis that nanoscale movements of molecular muscles can
be used to perform larger-scale mechanical work when attached
to solid substrates.
Classic stimuli-responsive molecular shuttles often act as
reversible molecular switches.517 In contrast, the system based
on rotaxane 309 (Figure 28), which was reported by Leigh and
4.3. Mobility of [c2]Daisy Chains
In addition to pseudorotaxanes and rotaxanes, another family of

threaded structures are described as daisy chains (Figure 29),
which have been constructed from self-complementary AB-type
plerotopic monomers, each of which contains two units: A as
the host part and B as the guest part.518523 The self-assemblies
can be either acyclic or cyclic daisy chain arrays, [a]daisy chains
or [c]daisy chains, respectively. The numerical descriptor refers
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Scheme 124. (a) A Bistable [3]Rotaxane-Based Linear Articial Molecular Muscle and (b) Graphical Representation of the
Proposed Operation Mechanism of a Molecular Device Based on This [3]Rotaxanea
Figure 28. Ratcheting a particle energetically uphill with a compartmentalized molecular machine and the structure of [2]rotaxane 309. Reproduced
with permission from ref 33. Copyright 2006 American Chemical Society.
applied for the preparation of [c2]daisy chains.524528 A

[c2]daisy chain prepared by Stoddart and co-workers was
based on the DB24C8/secondary ammonium salt recognition
to the number of monomer units that comprise any particular

superstructure. For example, a cyclic dimer is a [c2]daisy chain
(Figure 29). Various hostguest recognition motifs have been
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bidentate chelates, corresponding to the contracted situation

311. It meant that the rotaxane dimer was capable of stretching
and contracting at will under metal exchange.
On the basis of the interactions between DB24C8 and a
R2NH2+ unit or a Bpym2+ unit, an acidbase controllable
[c2]daisy chain was designed and synthesized by Stoddart and
co-workers.530 In this molecule, the two DB24C8 rings moved
between the two dierent recognition sites, R2NH2+ and
Bpym2+, under acidbase control (Scheme 126). The working
mechanism of this [c2]daisy chain was similar to the above
examples of molecular shuttles and could be named a molecular
muscle. There were two stable states, a contracted state and an
extended state during the movements of the ring. Under
normal conditions, the DB24C8 resided at the NH2+ center for
its better binding anity, and this was considered as the
extended state. When the ammonium center was deprotonated
by adding base, the ring slid to the bipyridinium unit, and this
was the contracted state. The lengths of the two states were ca.
3.1 and 2.2 nm, respectively. The synthetic strategy for this
acidbase controllable muscle molecule is possible to be
further functionalized and incorporated into liquid crystalline531
or polymeric532 systems.
All of the above-reported articial contraction/stretching
molecules can only change their lengths stepwise caused by
translocation of the ring parts between dierent guest moieties.
To mimic the unique spring-like function of biological
systems,535 Huang and co-workers prepared a molecular device
313 based on an amino-modied copillar[5]arene without
dierent guest moieties in the thread component.528 The length
of the device changed continuously as a spring when the
polarity of the solvent was changed (Figure 30). On the basis of
the investigation of pillar[5]arene/alkane pseudorotaxanes, it
was known that a guest containing a linear alkyl chain with four
methylenes usually showed a bigger binding constant than
Figure 29. Dierent types of daisy chains.
motif.518 Later, they applied crown ether/paraquat recognition

motifs to fabricate [c2]daisy chains.519 In 2000, Sauvage and coworkers prepared a linear rotaxane dimer driven by
coordination interactions.526 Very recently, Huang and coworkers reported two types of [c2]daisy chains based on the
benzo-21-crown-7/secondary ammonium salt recognition motif
and the pillar[5]arene/alkyl chain recognition motif, respectively.527,528
Given the intrinsic extension and contraction properties of
[c2]daisy chains (Scheme 125a), they are excellent building
blocks for the construction of articial molecular
muscles526533 and application in other areas, such as chemical
catalysts.534 To simulate real muscles, Sauvage and co-workers
designed a mechanically interlocked system, in which two linear
components glided along one another but stayed together
because of the rotaxane nature of the system.526,529 The
hermaphrodite monomer contained a coordinated macrocyclic part and a linear part incorporating simultaneously a fourcoordinate and a ve-coordinate metal center. The molecular
muscle was initially synthesized in its extended conformation
310, in which the two CuI centers were coordinated to the fourcoordinate situation of the axle (Scheme 125b). When the
system was demetallized and subsequently remetalated with
ZnII, the metal centers became coordinated to the three
Scheme 125. (a) Extended and Contracted Movements of a [c2]Daisy Chain and (b) a Molecular Muscle Based on the Metal
Coordination Systema
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Scheme 126. Formation of a pH-Controllable [c2]Daisy Chain 312a
similar compounds with longer or shorter alkyl chains.270,536,537

It was concluded by the 1H NMR signals of the encapsulated or
free protons that when a pillar[5]arene was swaying along a
guest with a long linear alkyl chain, the cavity was statistically
located on the four methylenes whose protons showed
relatively larger upeld shifts in solution. From this method,
the length of this molecular spring was calculated. In CDCl3, it
was in a contracted state with a length of about 31 . In
DMSO-d6, it was in an extended state with a length of 37 .
This work not only provided a useful method to investigate the
relative motion of a pillararene-based molecular switch, but also
oered a basis for the construction of an environmentally
responsive interlocked polymer that could mimic the biologic
contraction/stretching process.
5. APPLICATIONS OF PSEUDOROTAXANES AND

ROTAXANES
Figure 30. Molecular structure of a copillar[5]arene-based rotaxane
dimer 313 and schematic presentation of its vibration motion.
5.1. Protection of Encapsulated Molecules
5.1.1. Unstable Species. When linear molecules are

encircled by macrocycles, they are laid under a specic
environment provided by the wheel components, which may
change the properties of the encircled molecules, such as
Scheme 127. Rotaxane-Stabilized Thiophosphonium Salt from Disulde and Phosphine
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enhancement of uorescence signals, transformation of selfassembly morphologies, and activation and stabilization of
drugs.538542 In 1999, Vogtle and co-workers investigated the
inuence of the ring on the rate of chemical reactions of
rotaxanes.543 It was found that, due to the steric hindrance of
the wheel, the rates of hydrogenation of rotaxanes were
substantially lower than those of hydrogenation of free axles. In
other words, the rotaxane wheels provided noncovalent
protecting groups to decrease the activity of functional groups
in the central part.
The rotaxane structures also have the capability of stabilizing
unstable species. For example, an alkylthiophosphonium salt,
which was hard to isolate, acted as a key intermediate in the
desulfurization of dialkyl disuldes with phosphines.544
However, using a rotaxanated form, a stable thiophosphonium
salt 3152PF6 was isolated successfully through the reaction of a
rotaxanated disulde with hexamethylphosphorus triamide
(Scheme 127). The structure of the thioposphonium salt was
conrmed by spectroscopic and X-ray crystal structure analysis.
An interesting contrast is the reduced acidity of secondary
ammonium salts of DB24C8/sec-ammonium hexauorophosphate (PF6)-type rotaxanes reported by Takata and coworkers.545547 By exchanging the counteranion PF6 for the
uoride anion, they successfully isolated nonionic free secamine-type rotaxanes.547 This counteranion-exchange method
for neutralization of the ammonium rotaxanes decreased the
cationic character of the ammonium moiety and produced the
unusual sec-amine-type rotaxanes.
Kim and co-workers reported a U-shaped conformation of a
bolaamphiphile embedded in CB[8] (Scheme 128).548 With
back to last century, when azo dye-based dumbbell compounds

were encircled by CDs.373 As compared to nonrotaxanated
dyes, the rotaxanated dyes, which were permanently protected
inside the cavities of CDs, showed good solubility in most
solvents, and less aggregation in water.164 Because dyes are
often covalently attached to solid substrates for application,
whether the encapsulation of dye molecules on surfaces by
macrocycles can improve the longevity of the azo chromophore
or not sounds like a very important question. The problem was
addressed clearly by the synthesis of a chlorotriazine-functionalized azo dye rotaxane in 2001.373 This reactive dye rotaxane
displayed enhanced stability toward reductive bleaching.
Besides enhanced stability, dye rotaxanes also provide a
versatile approach to control of interfacial charge transfer,
which has been utilized to construct molecular-level insulation.
For example, Haques group presented an eective strategy
based on dye rotaxanes for the immobilization of azo dyes on
nanocrystalline TiO2 electrodes (Figure 31).549 After the dye
Scheme 128. U-Shaped Conformation of a Bolaamphiphile

Embedded in CB[8]a
Figure 31. Insulated dye on TiO2 electrodes based on rotaxane 317.

molecules were encapsulated by CD molecules, the interaction

between the TiO2 semiconductor surface and dye molecule was
limited, allowing control of interfacial charge recombination.
Such CD threaded sensitizer dye rotaxanes can not only
provide a shell to increase the stability of dyes, but also oer a
physical barrier to charge combination. In addition, the driving
force for dye adsorption on a nanocrystalline TiO2 lm was also
provided by the hydrophilic outer surface of CD.
Besides azo dye rotaxanes, uorescent dyes such as
cyanines,174 stilbenes,163 and acetylenes550 have also been
encapsulated within CDs and behaved dierently when trapped
inside the macrocyclic cavity. For example, their uorescence
eciency and photostability increased, their reversible redox
processes were exhibited, their kinetic stability was enhanced,
and their uorescence quenching was reduced. For cationic
rhodamine 6G, cucurbit[7]uril acted as its receptor to form an
inclusion complex, which allowed the development of a
supramolecular dye laser with environmental and safety
benets, high lasing eciency and stability, and an impressive

the stable conformation of the long alkyl chain of the guest 316,
a [2]pseudorotaxane complex would be expected. However,
when CB[8] and the guest were mixed together in a molar ratio
of 1:1, the long alkyl chain of the guest adopted a U-shaped
conformation inside the CB[8] cavity along with two positively
charged ammonium groups interacting with the same carbonyllaced portal of CB[8]. The discovery of the unconventional
conformation of 316 in the macrocycle not only sheds light on
the unusual architecture of archaebacterial membranes, but also
may provide an opportunity to design molecular knots,
machines, and switches.
5.1.2. Dyes. Macrocyclic molecules in rotaxanes can serve as
protectors for dyes. An early example of dye rotaxanes traced
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beam shape.551 All of these features provide the dyes with

numerous practical applications.
Squaraines are a family of uorescent near-IR dyes with
specic photophysical properties for wide applications such as
imaging, nonlinear optics, photovoltaics, and ion sensing.552
However, their inherent reactivity with nucleophiles and the
tendency to form nonuorescent aggregates in water limit the
use of these dyes.553 To improve the chemical stability and
photophysical properties of the dyes, some squaraine-derived
rotaxanes have been developed by Smith and co-workers in
recent years, which provided an eective approach to protect
the dyes.554,555 The rst type of wheel-like molecule, which was
used to construct these rotaxanes, was tetralactam macrocycle
(Scheme 129).554,556 With the squaraine unit as the template
based on the bifurcated hydrogen bonding between the 1,3dicarboxamide moieties and the squaraine oxygens, rotaxanes
319a and 319b were obtained through the clipping method.
There were several advantages for squaraine dyes after
formation of rotaxanes. The encapsulating macrocycle altered
the photophysical properties of a squaraine dye by inducing
red-shifts in its absorption/emission wavelengths, and stabilization of the squaraine excited state by electronic reorganization
of the surrounding macrocycle.557 Meanwhile, solvent-induced
quenching was reduced due to the deep encapsulation of the
dye inside the macrocycle. Furthermore, the chemical stability
of the squaraine was greatly increased when the rotaxane
formed. For example, it prevented the dye from nucleophilic
attack and aggregation and made its color remain for many
weeks.
By a similar strategy, other macrocycles were designed and
synthesized to encapsulate squaraines.558561 Investigations on
these rotaxanes indicated that squaraine encapsulation also
occurred in highly competitive media such as mixed aqueous/
organic solutions, vesicle membranes, and the organelles within
living cells.558 The protection role in stabilizing the chemical
and physical properties of squaraine dyes was maintained. A
rotaxane with an anthracene-containing macrocycle produced
more red-shift in absorption/emission wavelengths, while
another tetra(iodo)-substituted squaraine rotaxane demonstrated remarkable photostability, very high resistance to photobleaching.562
Formation of rotaxanes also helps squaraine dyes to achieve
some challenging tasks. For example, squaraine-rotaxanes 320a
and 320b (Figure 32a) had tremendous promise as extremely
stable near-infrared uorescent probes for in vitro and in vivo
optical imaging of live and xed cells (Figure 32b) and living
mice (Figure 32c). They were considered to be superior
substitutes for sulfonated carbocyanine dyes in many
biotechnology and imaging applications.563,564
Scheme 129. Formation of Squaraine-Based Rotaxanes 319a

and 319b
Figure 32. (a) Chemical structures of squaraine-based rotaxanes 320a and 320b; (b) uorescence-microscopy image of live mammalian cells treated
with 320a; and (c) optical image of a live mouse with subcutaneous injections of S. aureus and E. coli bacteria that were prelabeled with 320b.
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interactions have been used in great convenience.81,136,587590

For example, Huang and co-workers reported dynamic
supramolecular polymers that have linear or cross-linked
topologies.588 The linear supramolecular polymer was rst
obtained by self-organizing a heteroditopic monomer 322 with
a bridging ligand driven by hydrogen bonding and face-to-face
-stacking interactions between the cryptand host part and
paraquat derivative guest part on the monomer. Coordinating
the triazole ligand on this monomer with PdCl2(PhCN)2 then
aorded a cross-linked supramolecular polymer network
(Figure 34). Furthermore, the linear chains were restored
5.2. Stimuli-Responsive Supramolecular Polymeric

Materials
Supramolecular materials, with components bridged by

dynamic and reversible noncovalent bonds, have had a strong
impact on materials science accordingly.43,44,565568 Because of
their stimuli-responsive properties, pseudorotaxanes play a very
important role in the construction of supramolecular
polymers,569576 making them unique candidates for supramolecular materials. In the 1990s, Gibson and co-workers
constructed a series of linear, branched, or cross-linked
polypseudorotaxanes and polyrotaxanes.577579 Using the
dynamics of threading/dethreading of the macrocycles, they
found a method to measure polymer molecular weights.577
They also investigated the solvent switchable properties of the
supramolecular polymers.473,578,579 In the polyurethanes/crown
ethers systems, the crown ethers are localized at the NH groups
by hydrogen bonding in CHCl3, while they are delocalized
(mobile) but removed from the NH groups in DMSO.473
A variety of noncovalent interactions can be used to bring the
building blocks together to prepare supramolecular polypseudorotaxanes. Taking hydrophobic interaction, for example, CDs
and CB[n] are ideal and widely used macrocyclic hosts for
supramolecular polymers because of their hydrophobic cavities,
which can selectively bind guest molecules.580586 Zhang and
co-workers elegantly utilized CB[8] to bind a multifunctional
monomer 321 for the fabrication of supramolecular polymers
(Figure 33) based on multiple host-stabilized charge-transfer
Figure 34. Chemical structure of heteroditopic monomer 322 and

cartoon representation of the metal-coordination-based reversible
control of the supramolecular polymer topology. Reproduced with
permission from refs 40 and 588. Copyright 2012 Royal Society of
Chemistry and 2010 Wiley-VCH Verlag GmbH & Co. KGaA,
Weinheim.
again by the addition of a competitive ligand, PPh3, to trap the

cross-linker. This orthogonal noncovalent interaction strategy
provides an eective method for the topological control of
supramolecular polymers.
On the basis of dierent noncovalent interactions and the
structures of the building blocks, there exist various
responsivenesses of the resultant supramoleclar polymeric
materials to surrounding environments. First, thermoresponsiveness is one of the fundamental and most accessible
properties of supramolecular polymeric materials as weak
noncovalent interactions are inherently susceptible to thermal
stimuli. For example, a thermosensitive supramolecular polymer
hydrogel was reported recently by Scherman and co-workers,
which was obtained by recognizing the pendant paraquat units
on multivalent copolymer 323 and NAP moieties on copolymer
324 by the host molecule CB[8] to facilitate reversible crosslinking of the two copolymers (Figure 35a).591 The resultant
supramolecular hydrogels showed intermediate mechanical
properties (plateau modulus = 350600 Pa and zero-shear
viscosity = 555 Pas) based on the rheological characterization
at 5 wt % of the polymers in water. Moreover, the hydrogels
exhibited thermal reversibility because of the dynamic crosslinks (1:1:1 supramolecular ternary complexes of CB[8]/
paraquat/NAP), which could be qualitatively characterized by
probing the hydrogel microstructures. Upon heating, the
hydrogel underwent a gel-to-sol transition, which was reversed
upon cooling or adding more CB[8] (Figure 35b).
Figure 33. Cartoon representation of the formation of a CB[8]-based

water-soluble supramolecular polymer. Reproduced with permission
from refs 40 and 586. Copyright 2012 Royal Society of Chemistry and
2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
interactions in water. Such polymers could form a potassium

cation-responsive supramolecular gel at a low concentration (4
mM).586 Therefore, by tuning the stimuli-responsive properties
of self-complementary molecules, water-soluble potassium
cation-responsive supramolecular polymeric materials driven
by hydrophobic interactions can be easily obtained.
To build highly complex and multifunctional supramolecular
polymers, either self-sorting organization of two heteroditopic
monomers or the combination of multiple noncovalent
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links for supramolecular polymer gels by changing the solution

pH, such as in the DB24C8/dibenzylammonium salt
systems.595 As a challenge to the formation of supramolecular
polymer gels from low-molecular-weight molecules, Huang and
co-workers prepared a heteroditopic monomer 326 comprising
the reversible hostguest recognition motif between the
DB24C8 unit and its complementary guest dibenzylammonium
salt moiety linked by a long aliphatic chain (Figure 37).598 Selfassembly of this monomer in solution produced a linear
supramolecular polymer, and then formed an entangled threedimensional ber network, resulting in gelation. Furthermore,
reversible gelsol transitions were realized by subsequent
alternation of heating and cooling, or acidication and
neutralization. More importantly, the dual-responsive supramolecular polymer gel was successfully employed in the
controlled release of rhodamine B. Another monomer
containing a triptycene-derived polyether moiety and two
dibenzylammonium salt units designed by Chen and coworkers was also used to form a dual-responsive supramolecular
polymer network gel.599 These two studies demonstrated that
functional smart materials can be constructed by rational design
of low-molecular-weight building blocks.
Besides pseudorotaxanes, the [c2]daisy chains and rotaxanes
can also be incorporated into supramolecular polymeric
materials, allowing regulation of mechanical properties by
transforming motions of these MIMs at the molecular
level.600,601 Grubbs and co-workers prepared mechanically
interlocked supramolecular polymers from the polymerization
of [c2]daisy chains by using ring-closing metathesis.602
Subsequently, with the aim to create muscle-like supramolecular polymeric materials, Stoddart and co-workers
reported a linear, mechanically interlocked, main-chain polymer
with repeated bistable [c2]daisy chains incorporated (Figure
38).522 The [c2]daisy chain molecule 327 had propargyl groups
on its stoppers, which underwent reversible extension and
contraction upon exposure to external stimuli. This dialkynefunctionalized [c2]daisy chain AA monomer then was subjected
to step-growth polymerization with a diazide BB monomer
employing click chemistry. The resultant bistable poly[c2]daisy
chain 328 was analyzed by size exclusion chromatography/
multiangle light scattering, showing that this polymer had a
molecular weight (Mn) of 33 kDa and a polydispersity of 1.85.
This Mn value demonstrated that each polymer chain was
composed of about 11 repeating units. The acid/base
controlled extension and contraction behavior of both the
monomer and the polymer were studied in solution by 1H
NMR spectroscopy, UV/vis absorption spectroscopy, and
cyclic voltammetry. The [c2]daisy chains and their polymeric
derivatives underwent quantitative, ecient, and reversible
extension and contraction processes in solution. The kinetics of
the acid/base-induced switching processes on the basis of the
measurements of stopped-ow spectrophotometry showed that
the switching rates for the extension/contraction processes of
polymeric [c2]daisy chain were faster than those of its
monomeric counterpart. From this valuable example, we can
conclude that movements at the molecular level can lead to
changes in macroscopic material properties.
Polyrotaxanes have become a hot topic in polymer chemistry
and materials science because of their unique topologies and
properties.603609 Early examples attempted to construct crosslinked polyrotaxanes. For example, Gibson and co-workers
prepared macromolecular knitting by self-assembly of poly[bis(5-methylene-1,3-phenylene)-32-crown10 sebacate] and pre-
Figure 35. (a) Chemical structures of polymers 323 and 324 and
cartoon representation of the formation of a 3D network cross-linked
by CB[8]; (b) illustration of the thermal reversibility of the
supramolecular polymer network hydrogel demonstrated by SEM
images. Reproduced with permission from refs 40 and 591. Copyright
2012 Royal Society of Chemistry and 2010 American Chemical
Society.
Second, photoresponsive supramolecular polymer gels have

been widely fabricated on the basis of azobenzene-type
derivatives.592,593 A beautiful example was reported by Jiang
and co-workers through the association/dissociation of the
pseudorotaxane-containing azobenzene-type derivative 325 and
-CD.594 Initially, the self-assembly of poly(ethylene glycol)
and -CD formed a pseudopolyrotaxane hydrogel. After
addition of water-soluble competitive guest 1-[p-(phenylazo)benzyl]pyridinium bromide trans-325 and ultrasonication, the
gel turned into a transparent sol in a few minutes (Figure 36)
due to the stronger hostguest interactions between trans-325
and -CD. Using photoisomerization of the azobenzene moiety
upon UV (365 nm) irradiation, the -CDtrans-325 complex
dissociated and then -CD returned to the PEG chain,
reforming the hydrogel. The reversible process was achieved
by visible light irradiation. The photoresponsive gel to sol and
sol to gel transitions could be repeated for several cycles
without any disturbance.
Third, chemoresponsiveness is still a fascinating property,
which makes some applications of responsive supramolecular
polymeric materials possible.595597 Some early successful
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Figure 36. Cartoon representation of photoresponsive gelsolgel transitions driven by competitive inclusion complexation. Reproduced with
permission from refs 40 and 594. Copyright 2012 Royal Society of Chemistry and 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
cooperatively.609 This gel has good tensility, low viscosity, and

large swellability in water.
Recently, Takata and co-workers reported the synthesis of a
type of graft polyrotaxanes (GPR) 329 by empolying the
grafting-onto protocol to a polypseudorotaxane and analyzing
its structural characteristics and dynamic behavior.600 Mixing
poly(DB24C8) (Mn = 4000, PDI = 1.35) with an equimolar
amount of secondary ammonium salt in CH2Cl2 produced the
polypseudorotaxane. Polyrotaxanes 329 were prepared by
subsequent addition of the polytetrahydrofuran grafting agent
(Figure 39). To achieve high mobility of the graft chain
GPRH2PF6, N-acetylation of the polymer was performed to give
GPRAc. The GPRAc was obtained in 94% yield by treatment of
GPRH2PF6 with acetic anhydride (Ac2O) and triethylamine at 60
C for 3 days. The movement of the DB24C8 wheel to the
polytetrahydrofuran moiety was conrmed by 1H NMR
spectroscopy and other techniques. Because of the host
guest recognition, the secondary ammoniun salt part of the
graft chain was located in the crown ether cavity of the main
chain for the polymer GPRH2PF6. After N-acetylation, the graft
chain length of GPRAc obviously increased because of the
enhanced mobility or free translation of the graft chain. The
mobile rotaxane connection decided the dynamic property of
the polyrotaxanes as compared to traditional graft copolymers,
which allowed them to be applied in advanced supramolecular
materials.
Fourth, redox-responsive supramolecular polymeric materials
can be constructed and manipulated.610,611 Harada and coworkers synthesized poly(acrylic acid) (Mw = 2.5 105)
modied with -CD units as a host polymer 330 and with
ferrocene moieties as a guest polymer 331. Using versatile
hostguest interactions inherent with easily tuned switching
eciencies and functions, self-healing supramolecular polymeric materials were prepared (Figure 40).612 Hydrogelation
led to an increase of the viscosity of the solution when a 1:1
mixture of a solution of host polymer 330 and guest polymer
331 in a pH = 9 boric acid/KCl/NaOH buer solution was
prepared. Further studies showed that hostguest comple-
Figure 37. (a) Cartoon representation of the formation of a linear

supramolecular polymer from a heteroditopic monomer 326; and (b)
illustration of dual-responsive supramolecular polymer gelsol
transitions and supramolecular polymer aggregates (glue-like viscous
liquid and transparent lm). Reproduced with permission from refs 40
and 598. Copyright 2012 Royal Society of Chemistry and 2011 WileyVCH Verlag GmbH & Co. KGaA, Weinheim.
formed polyurethane containing paraquat moieties in tetrahydrofuran.608 The branching process was reversible depending
on the solvent and temperature. Okumura and co-workers
reported a polyrotaxane gel by gure-of-eight cross-links acting
like pulleys to equalize the tension of the polymer chains
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Figure 38. Chemical structures of [c2]daisy chain 327 and poly[c2]daisy chain 328 and cartoon representation of the acidbase switching process of
328. Reproduced with permission from refs 40 and 522. Copyright 2012 Royal Society of Chemistry and 2009 American Chemical Society.
Figure 39. Chemical structures of GPRH2PF6 and GPRAc. Reproduced

with permission from ref 40. Copyright 2012 Royal Society of
Chemistry.
mentarity and multipoint cross-links have cooperative roles in

forming the supramolecular polymer network hydrogel. The
reversible gelsol transitions were achieved by adding oxidant
(NaClO aq) and then reductant (glutathione, GSH). Moreover, electrochemical oxidation also transformed the supramolecular polymer hydrogel into the sol. Subsequent reduction
by heating the sol at 50 C recovered the hydrogel. The
dynamic reversible nature of the hostguest interactions
between the side chains of both polymers determines the
self-healing property of the supramolecular polymer network
(Figure 40a). This was proved by rheological experiments. A
cube-shaped supramolecular polymer hydrogel was cut in half,
and then rejoined. After standing for 24 h, the crack
disappeared, and the sample hydrogel suciently healed to
Figure 40. (a) Chemical structures of host polymer 330 and guest
polymer 331 and schematic representation of the redox-responsive
supramolecular polymer network prepared from self-assembly of them;
and (b) cartoon representation of the self-healing process of the
supramolecular polymer network. Reproduced with permission from
refs 40 and 612. Copyright 2012 Royal Society of Chemistry and 2011
Nature Publishing Group.
form one gel (Figure 40b). What is more interesting is that the
self-healing property of the hydrogel could be controlled by
redox reactions. If the cut surfaces of the hydrogel were coated
with an aqueous solution of oxidant (NaClO, 7 mM, 20 L),
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healing did not occur upon attaching the two pieces together.
However, the healing was observed by spreading reductant
GSH aq (20 mM, 20 L) onto the oxidized cut surface and
allowing the hydrogel to stand for 24 h. This elegant study
represents a good example of self-healing supramolecular
polymeric materials based on hostguest interactions and will
further prompt the application of hostguest chemistry in the
fabrication of advanced supramolecular polymeric materials.
Using the same hostguest recognition motif, Yuan and coworkers prepared redox-responsive supramolecular diblock
copolymer vesicles in aqueous solution by self-assembling two
end-decorated homopolymers, polystyrene--cyclodextrin and
poly(ethylene oxide)-ferrocene.613 Interestingly, the assembly
and disassembly speeds of the supramolecular vesicles were
controlled by changing the applied voltage. Furthermore, the
supramolecular vesicles acted as nanocapsules carrying
molecules within their hollow cavities, and the voltage regulated
the drug release time. This valuable example represents the
possibility of employing supramolecular nanocapsules in
electrochemical therapeutics.
Multiresponsive supramolecular polymeric materials give rise
to more exibility for the construction of intelligent
materials.614621 This can be achieved by consummate
integration between the material structures and the environmental responsiveness of noncovalent interactions. Recently,
Huang and co-workers reported a quadruple-responsive
supramolecular polymer network gel constructed by orthogonal
self-assembly, which showed good shape-persistent and elastic
properties.615 Heteroditopic monomer 332 contained a 1,2,3triazole group between the B21C7 host unit and its
complementary dialkylammonium salt guest moiety. Selfassembly of this monomer in solution formed a linear
supramolecular polymer driven by the hostguest interactions
between the B21C7 unit and dialkylammonium salt moiety. A
supramolecular polymer network gel then was obtained by
adding a cross-linker (Figure 41), [PdCl2(PhCN)2], to the
linear supramolecular polymer solution because the 1,2,3triazole group acted as a ligand for coordination with
palladium(II). The gel exhibited a reversible gelsol transition
in response to quadruple distinct stimuli (pH-, thermo-, cation-,
and metallo-induced) (Figure 42). Generally, pH- and thermoinduced gelsol phase transitions of supramolecular polymers
are facile by adding base and acid or heating and cooling.
Herein, the cation- and metallo-induced gelsol phase
transitions are unique by adding K+ to prevent the formation
of supramolecular polymers or adding the competitive ligand
PPh3 for the cross-linker to deconstruct the supramolecular
polymer network. The net-like morphology of the supramolecular polymer gel was controlled by the amount of crosslinker added to the system, and the material could be molded
into shape-persistent, free-standing objects with elastic
behavior. These features were totally due to the dynamically
reversible hostguest complexation and good mechanical
properties of the cross-linked polymer network, making this
supramolecular polymer gel an unprecedentedly intelligent soft
material. Furthermore, the same research group has also used
the same monomer 332 to prepare supramolecular polymer
nanobers via the electrospinning technique620 and obtain
adjustable supramolecular polymer microstructures by a breath
gure method.621
Figure 41. Cartoon representation of the formation of linear and

cross-linked supramolecular polymers from monomer 332. Reproduced with permission from refs 40 and 615. Copyright 2012 Royal
Society of Chemistry and 2012 Wiley-VCH Verlag GmbH & Co.
KGaA, Weinheim.
Figure 42. Reversible gelsol transitions of the supramolecular

polymer network gel 332 triggered by four dierent stimuli (pH-,
thermo-, cation-, and metallo-induced). Reproduced with permission
from refs 40 and 615. Copyright 2012 Royal Society of Chemistry and
5.3. Applications of Rotaxane-Based Molecular Machines
As described in the above section, component parts of

rotaxanes can undergo controllable and reversible motions
without damaging their mechanically interlocked structures.
Therefore, rotaxanes have potential applications in the
development of articial molecular devices. Numerous
examples of molecular machines based on pseudorotaxanes
and rotaxanes in solution have been successfully reported.
However, most useful molecular devices generally work in the
solid state, at interfaces or on surfaces. To make these
molecules useful for practical applications, the rst important
thing is to transfer molecular-machine technology from solution
to solid substrates or surfaces. It is very challenging work
because the behavior of rotaxane systems on solid supports
must be dierent from that observed in solution. Several new
questions have to be addressed: (i) Will these mechanically
interlocked systems still move on solid supports just like what
they do in solution? (ii) How does one analyze these new
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Figure 43. Chemical structures of rotaxanes 333 and 334 used in the molecular devices.
Figure 44. Chemical structures of [2]pseudorotaxane 335 and [2]rotaxane 336.
Figure 45. Chemical structure of the [2]rotaxane 337 used in the crossbar memory.
switches and gates have been already demonstrated in the

solution phase. With a dierent operation mechanism from the
above examples, Stoddart, Heath, and co-workers reported
redox-active, degenerate, two-station, and V-shaped [2]rotaxane
333 and [3]rotaxane 334 (Figure 43) as a monolayer between
electrodes made from titanium and aluminum oxide.622,623
These solid-state molecular electronic devices can be
congured to generate AND and OR logic functions. On the
basis of the LangmuirBlodgett monolayer of the compounds,
single-molecule-thick electrochemical junctions were fabricated
and showed their transport properties.
The strategy for the LB monolayer formation based on
[2]pseudorotaxanes and [2]rotaxanes has also been utilized to
develop solid-state molecular switch tunnel junction devi-
functional materials and their dynamics? (iii) Do the threaded

molecules have preferential orientation on solid supports,
which is required for large-amplitude motions in macroscopic
world? To our delight, there are already some examples of
switchable and detectable supramolecular machines that have
been constructed into molecular devices through suitable
engineering.
5.3.1. Molecular Electronic Devices Based on the
LangmuirBlodgett Monolayers. The LangmuirBlodgett
(LB) technique is an elegant approach to arranging molecules
into well-organized monolayers and multilayered lms, which
can be widely applied to create ultrathin lms with a specic
architecture that can be used as chemical sensors, modied
electrodes, or molecular electronic devices.622 Rotaxane-based
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ces.624626 For example, one such device was developed on the

basis of the [2]pseudorotaxane 335 and [2]rotaxane 336
incorporating both hydrophobic and hydrophilic regions to
allow self-organization (Figure 44).624 The electrical properties
were found to be highly dependent on the supramolecular
structure, the presence of bistability within the (super)molecule, and the organization of the LB lm. The device
exhibited a (noncapacitive) hysteretic currentvoltage response
that switched the device between high- and low-conductivity
states, although control devices exhibited no such response.
This study represents a signicant step toward elucidating
molecular structure/device property relationships for active
molecular electronic devices.
Later, with a monolayer of bistable [2]rotaxane 337
containing both hydrophobic and hydrophilic regions (Figure
45) as the data storage elements, Stoddart, Heath, and coworkers developed a 160-kilobit molecular electronic memory
circuit fabricated at a density of 1011 bits cm1 (pitch 33 nm;
memory cell size 0.0011 m2).627 This memory circuit has
achieved the dimensions of a dynamic random access memory
circuit projected to be available by 2020. This proves that it is
feasible and promising to use molecules as nanoscale
components to create miniaturized electric circuits and develop
molecular computing.
5.3.2. Rotaxane-Based Molecular Machines on Surfaces. Surface assembly of mechanically interlocked molecular
systems628631 aords the platform to utilize the motional
characteristics of these molecules in electronics, data storage,
and macroscale devices. Gokel, Kaifer, and co-workers reported
a catenane that was attached to an electrode surface through a
[2]pseudorotaxane intermediate.632 The bis-thiolated axle in
the pseudorotaxane complex was assembled on a gold surface,
which resulted in the formation of an interfacial structure
containing two mechanically interlocked components. The
preparation of layers of pseudorotaxanes or rotaxanes on a gold
surface was reported in 2003.633,634 One end of the axle for the
threaded molecules involving a disulde group or a thioctic
ester derivative was anchored to a gold surface, which played
the role of a stopper for the system (Figure 46).633
consisting of a crown ether ring and a disulde-containing axle

attached on a gold surface.637 Recently, total internal reection
uorescence microscopy (TIRFM) allowed the observation of
rotary movement of a ring in a single rotaxane molecule
immobilized on a glass substrate.165 These techniques are very
useful for the identication of the mechanically anchored units
on the surfaces. Further eorts have focused on achieving
mobility of surface conned supramolecular architectures.
Some related examples of rotaxane-modied surfaces with a
machine-like function and practical applications will now be
discussed.
5.3.2.1. Self-Assembled Monolayers on Gold Surfaces. A
number of redox-active switchable rotaxanes on gold electrodes
have been constructed, and their shuttling performances have
been studied by chronoamperometric experiments.638643 On
the basis of this strategy, Willner and co-workers designed and
prepared a [2]rotaxane electron relay 339 interlocked on a
molecular wire connecting the enzyme to the electrode.641 It
was used for the electrical contacting of a redox enzyme. In this
system, the tetracationic cyclophane unit was used as an
electron-transfer mediator for the wiring of the enzyme glucose
oxidase (GOx). The adamantane was used as a stopper for the
rotaxane, which was substituted by a bulky avin adenine
dinucleotide (FAD) unit that was recognized by apo-glucose
oxidase (apo-GOx) (Figure 47). The shuttling motion of this
system was triggered by the reduction and oxidation of the
FAD unit. Because of the shuttling movement, the interlocked
macrocycle transported electrons from the reduced FAD
cofactor to the electrode surface, so the bioelectrocatalytic
oxidation of glucose was achieved.
An ion gate was reported by Kim and co-workers based on
the pH-driven CB[6]-based systems.644 In this regard, SAMs
were obtained by immersing a gold electrode in an aqueous
solution containing pseudorotaxane 340. Complex 340
consisted of a CB[6] unit and a linear molecule with a 1,4butanediammonium station and a 1,2-dithiolane tethering unit
(Figure 48). Dethreading/rethreading of CB[6] was achieved
upon addition of NaOH and NH4Cl, respectively. When the
supramolecular complex was in the threading coconformation,
[Fe(CN)6]3 anions were prevented from reaching the
electrode surface, while dethreading the macrocycle resulted
in the accessibility of [Fe(CN)6]3 anions to the electrode
surface, and thus the redox reaction took place.
Functionalization of surfaces with pseudorotaxanes or
rotaxanes has also found applications in the eld of chemical
sensing.645,646 In 2007, Beer and co-workers reported SAMs
based on redox-active bisferrocene-functionalized [2]rotaxane
341, which was capable of selectively sensing chloride ions
electrochemically (Figure 49). Using chloride anion as a
template, the pseudorotaxane was initially self-assembled in
solution from an anion binding macrocycle with an appended
ferrocene redox-active center and an ion-paired thread with a
bulky ferrocene redox-active stopper group at one terminus.
The pseudorotaxane was subsequently grafted onto a gold
surface by immersing a gold electrode into the solution. This
system exhibited highly selective sensing for chloride as
compared to other anions, such as H2PO4, HSO4, or Br,
which was demonstrated by monitoring the electrochemical
response of the ferrocenyl-appended redox centers of the SAM.
The attachment of stimuli-responsive molecular shuttles on
surfaces can result in macroscopic switchable surfaces. For
example, a monolayer of a light-switchable bistable [2]rotaxane
provided a photoresponsive surface on which the millimeter-
Figure 46. Copper-complexed rotaxane 338 on a gold surface.
The early surface-attached rotaxanes have often been studied

by cyclic voltammetry. Besides, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and Fourier
transform infrared spectroscopy (FTIR) have also been used to
determine whether rotaxanes have been attached onto the
surfaces.635,636 In the work by Vance and co-workers, X-ray
absorption spectroscopy (XAS) and X-ray photoemission
spectroscopy (XPS) were utilized to characterize a rotaxane
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Figure 47. Bioelectrocatalytic oxidation of glucose mediated by a GOx-FAD-reconstituted redox switchable rotaxane 339 on an Au electrode.
Figure 48. SAM of a pH-responsive CB[6]-based pseudorotaxane 340

on Au. Reproduced with permission from ref 644. Copyright 2003
Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Figure 50. Chemical structure of switchable uorinated molecular

shuttle 342 and graphical representation of a photoresponsive surface
based on 342. Reproduced with permission from ref 647. Copyright
2005 Nature Publishing Group.
station to (Z)-maleamide. This bistable [2]rotaxane was

physisorbed to the surface of a carboxylic acid-terminated
SAM of 11-mercaptoundecanoic acid (MUA) on Au(111)
deposited on glass or mica by hydrogen bonding between the
pyridine nitrogens of the macrocycle and the carboxylic acid
groups of the monolayer. The biased Brownian motion of the
components of photoresponsive rotaxane 342 exposed or
concealed uoroalkane residues and modied the surface
tension. The molecular shuttles organized over surfaces
behaved coherently, and the collective nanoscale movements
of their mechanically linked components could be translated
into macroscopic motions.
Figure 49. Self-assembled monolayer of a redox-active ferrocenefunctionalized rotaxane 341 on Au.
scale directional transport of diiodomethane drops was

achieved (Figure 50).647 At rst, a tetraamide macrocycle
containing pyridine units encircled a linear fragment including a
tetrauorosuccinamide station and a photoisomerizable fumaramide station to form rotaxane 342, which was photoresponsive by photoisomerization of the (E)-fumaramide
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Figure 51. Graphical representations of operation of nanovalves based on CBPQT4+. Reproduced with permission from ref 649. Copyright 2004
5.3.2.2. Nanovalves on Silica Surfaces. The switching

properties of molecular machines based on pseudorotaxanes
make them excellent candidates for drug delivery. The release
of drugs can be easily controlled by the change of the states of
supramolecular systems, named nanovalves. It was shown by
Stoddart, Zink, and co-workers that a pseudorotaxane-based
machine successfully came into this function when it was
trapped physically in a rigid nanoporous solgel silica
framework or attached covalently to silica surfaces triggered
by photochemical stimuli.648 On the basis of this strategy, the
movement of the pseudorotaxane comprising of CBPQT4+ and
BHEEN in mesostructured silica acts as a nanovalve to close
the container with luminescent molecules trapped inside and
release them on demand (Figure 51).649 Before operating the
nanovalve, it is rst essential to make gateposts for the
nanocontainer with BHEEN attached to particles. The
hexagonal cylindrical nanopores are all ca. 2.0 nm in diameter.
The gate is closed by placing the lm in an aqueous solution of
CBPQT4+, resulting in encapsulating BHEEN derivatives,
which block the pore openings in the macrocycles to form
tethered pseudorotaxanes. After addition of NaBH3CN as a
relatively mild reducing agent, the Ir(ppy)3 molecules escape
from the containers because of the dissociation process caused
by reduction of the CBPQT4+ ring. In another mode of
operation, photosensitizers, such as 9-anthracenecarboxylic acid
and tethered [Ru(bpy)2(bpy(CH2OH)2)]2+ (bpy = 2,2bipyridine), are tethered and excited by light to transfer
electrons to nearby CBPQT4+ rings and reduce them, leading
to the dissociation.650 The method using light is less ecient at
activating the release of the guests.
To nd more ecient methodologies for opening the gate,
other supramolecular systems were functionalized to the
nanovalves, such as a DB24C8/dialkylammonium ion pseudorotaxane and a CD/polyethylenimine (PEI) polypseudorotaxane.651653 These nanosystems were controlled by pH
stimulation and competitive binding. For the CD/PEI system,
the guest molecules were entrapped in the pores of a
mesoporous silica particle (Si-MP) blocked by threading of
CDs onto the surface-grafted PEI chains at pH 11 (Figure
52).653 The CD/PEI polypseudorotaxane was dissociated when
the pH was 5.5, leading to the release of guests. This approach
Figure 52. Schematic presentation of pH-responsive release of guest

molecules from the nanovalves based on CD hosts. Reproduced with
permission from ref 653. Copyright 2007 Wiley-VCH Verlag GmbH &
Co. KGaA, Weinheim.
provided an eective route for CD-based polypseudorotaxanes

to various useful applications, including molecular machines,
stimuli-responsive nanocarriers, and sensors.
One of the far-reaching applications for nanovalves involves
delivering drugs and enzymes in biological environments.
Therefore, achieving the function of nanovalves in aqueous and
biological media has also been carried out successfully.654656
For example, the recognition motif based on CB[6] and a
tethered bisammonium unit was embedded into the chemically
stable mesoporous silica supports.654 The pseudorotaxane
system was associated by iondipole interactions and
dissociated by simply changing the pH in water, which resulted
in the operation of the nanovalves (Figure 53). Further
investigation indicated that the gatepost in shorter linker length
tightens up the nanovalves suciently to prevent leakage.
Because high pH was not suitable for biological applications,
the tethered linear molecules were subsequently changed to
trisammonium molecules.655 Thus, novel mechanized nanoparticles based on the interaction of CB[6] with a
trisammonium pseudorotaxane were reported, which operated
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Figure 53. Graphical representations of operating supramolecular nanovalves based on CB[6]. Reproduced with permission from ref 654. Copyright
Figure 54. Graphical representations of pH-responsive nanovalves based on -CD. Reproduced with permission from ref 657. Copyright 2010
nanoparticles (MSNP) loaded with Hoechst dye and the

anticancer drug doxorubicin were eciently taken up into
acidic endosomal compartments in human dierentiated
myeloid (THP-1) and squamous carcinoma (KB-31) cell
lines. When the mechanized silica was combined with zincdoped iron oxide, a new generation of drug delivery system was
created with heat-responsive activation.658 The nanovalve
attached to this system remained closed in biological
environments and opened on heating. These magnetic-core
silica nanoparticles were eective in delivering anticancer drugs
upon exposure to an oscillating magnetic eld.
Besides application in drug delivery, nanovalves consisting of
pseudorotaxane systems and mesoporous silica nanoparticles,
together with nanoimpellers attached in the supports,
functioned as AND logic gates relying on light and pH inputs
and provided sophisticated control of the contents of the pores
to encapsulate propidium iodide guest molecules at neutral pH

and then release the contents under mildly acidic conditions.
The very dierent basicity of the anilinium nitrogen atom from
the other two alkyl nitrogen atoms, the dierent lengths of the
oligomethylene spacers, and the functional group of terminal
phenyl unit are important features for adjusting the operation
of the nanovalves.
Recently, the feasibility of mesoporous silica nanoparticles
with nanovalves acting as drug delivery systems was
investigated.657659 To achieve the functions of gates in
biological systems, the nanovalve was designed to be closed
tightly at pH 7.4, but self-open in acidic endosomal
compartments (Figure 54).657 Therefore, a series of aromatic
amines were chosen as the stalk and -CD as the cap. The pHsensitive nanovalves then were fabricated and functioned as
drug delivery vehicles in cells. These mesoporous silica
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(Figure 55).660 Azobenzene motifs tethered to the inner pore

walls of the supports acted as nanoimpellers and could be
dierent linkers were employed to attach the bistable

[2]rotaxane molecules covalently to the silica substrate.661
Nanovalves with shorter linkers were less leaky. These
operational valves are true molecular machines consisting of a
solid framework with movable parts to accomplish a specic
task and may be used in the controlled release of drugs in the
future.
Later, the same group reported the design, synthesis, and
operation of enzyme-responsive snap-top covered silica nanocontainers.662 The [2]rotaxanes had an -CD wheel, a
poly(ethylene glycol) thread, and a cleavable stopper (Scheme
130). The device contained guest molecules within the pores
after formation of the rotaxanes; when cleavage of the stopper
happened, the guests were released due to the dissociation of
the pseudorotaxanes. It was indicated by luminescence
spectroscopy that the ester-linked snap-top system was
selectively activated by porcine liver esterase. However, the
amide-linked system was left intact. This biocompatible
controlled release system exploited enzymatic specicity. As
the stoppering units can be changed in a wide range, activation
of the stoppers can be easily chosen with various modes.
5.4. MetalOrganic Frameworks
Although a great number of investigations on the dynamic

properties of rotaxanes have been derived from solution studies,
there still exists a problem that the molecules are randomly
dispersed and their motion incoherent in solution. To solve this
problem, molecular machines on solid supports have been
developed.34,35 On the other hand, eorts have focused on
providing a platform for their strategic and precise placement in
two- or three-dimensional space so that they can achieve a
higher level of molecular organization. Metalorganic frameworks (MOFs) are a well-established class of crystalline
materials with ultrahigh porosity and enormous internal surface
areas consisting of organic linkers and inorganic metal nodes.663
To make the motion of rotaxanes coherent, the idea is that
incorporating rotaxanes into the struts of MOFs will introduce
dynamics onto their frameworks.36,664 It is an interesting and
challenging topic that provides a new perspective for rotaxane
chemistry.
The initial study on rotaxane-modied MOFs is based on the
preparation of 2D or 3D networks composed of organic
[2]pseudorotaxane subunits and linking metal centers.665669
Pioneering work by Kim and co-workers demonstrated that by
threading CBs with N,N-bis(4-pyridylmethyl)-1,4-diaminobutane dihydronitrate, followed by the reaction of the
pseudorotaxane 344 with Ag(CH3C6H4SO3) and AgNO3, 1D
and 2D coordination polymer networks were constructed
(Scheme 131).665 The X-ray crystal structure of 346 revealed
an unprecedented polyrotaxane in which cucurbituril beads
were threaded on a 2D coordination polymer network. The 2D
network consisted of large edge-sharing chair-shaped hexagons
with an Ag(I) ion at each corner and a [2]pseudorotaxane
subunit at each edge connecting two Ag(I) ions. The mean
length of the edge was 20.9 , and the mean separation of the
opposite corners was 38.0 .
Subsequently, 3D coordination polymer networks containing
binuclear lanthanide metal centers were obtained.666 The X-ray
crystal structures of the coordination polymers revealed that the
basic building unit of the framework consisted of a binuclear
Tb3+ center and six [2]pseudorotaxane units, each of which
contained 3-phenylcarboxylate groups at the terminals. The 3D
polymer network had an inclined -polonium topology with
Figure 55. Truth table for an AND gate based on dual-controlled

nanoparticles. (a) Excitation with 448 nm light; (b) addition of
NaOH; and (c) simultaneous excitation with 448 nm light and
addition of NaOH. Reproduced with permission from ref 660.
Copyright 2009 American Chemical Society.
interconverted between two congurations (trans and cis) upon

absorption of light. Also, the CB[6]/bisalkylammonium
[2]pseudorotaxanes tethered to the outer surfaces of the
nanoparticle supports acted as nanovalves and could be
associated and dissociated by pH stimuli. The movements
were based on entirely dierent principles. Excitation with 448
nm light induced the dynamic wagging motion of the
nanoimpellers, but the nanovalves remained shut and the
contents were contained. Addition of NaOH opened the
nanovalves, but the static nanoimpellers were able to keep the
contents contained. Only when both controlled release
mechanisms were activated simultaneously could the release
of the guest molecules be observed.
Nanovalves with pseudorotaxanes attached to the mesoporous silica particles were described above in detail. They
achieve their gating behavior based on the association/
dissociation movement of the supramolecular complex.
However, such nanovalves act like a cork in bottle; that is to
say, the trapped molecules can only be released from the
system but cannot be trapped again.650 Here, a reversible
molecular valve (Figure 56) was demonstrated on the basis of a
[2]rotaxane comprised of CBPQT4+ ring threaded onto an axle
with a TTF unit and a DNP site.298 The CBPQT4+ ring moves
back and forth on the axle by oxidation and reduction of the
TTF unit, resulting in the release and encapsulation of the
trapped molecules. Furthermore, by varying chain lengths,
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Figure 56. A reversible [2]rotaxane-based nanovalve. (a) The structural formula of the bistable [2]rotaxane; and (b) the proposed mechanism for
the operation of the nanovalve. Reproduced with permission from ref 298. Copyright 2005 American National Academy of Sciences.
Scheme 130. Synthesis and Activation of Enzyme-Responsive Snap-Top Systemsa
of Co 71%, and Zn 92%, respectively (Figure 57). The use of

CoII and ZnII ions in MeCN resulted in an octahedral
coordination geometry comprising two [2]pseudorotaxane
ligands, two MeCN molecules, and two water molecules all
with trans orientations. Because of the fact that the linker could
adopt only an anti conformation at the central ethylene unit
when threaded through DB24C8, it produced a linear 1D MOF
with a CoCo distance of 22.1 .
On the other hand, the reaction of 2 equiv of 347[BF4]2 with
4 equiv of DB24C8 and 1 equiv of [M(H2O)6][BF4]2 (M = Cu,
Cd, Ni) in noncoordinating solvent MeNO2 produced X-ray
quality crystalline materials (average yields 80%) of 2D MOFs
with square nets and formula {[Cd(H2O)(BF4)(RL1)2][BF4]5
(MeNO2)15}x (Figure 57). This octahedral coordination
binuclear terbium centers behaving as six-connected nodes. The

void space in the unit cell was lled with free [2]pseudorotaxanes, counteranions, and water molecules.
Loeb and co-workers demonstrated that [2]pseudorotaxanes
incorporating dipyridinium axles with DB24C8 wheels was
used to produce [2]rotaxanes with metal complexes as stoppers
in good yield.98 They further used the same supramolecular
motif in metalligand self-assembly (crystal engineering)
reactions and construction of rotaxane-modied MOFs (Figure
57).667,668 On one hand, when 1 equiv of 347[BF4]2 was mixed
with 2 equiv of DB24C8 and 1 equiv of [M(H2O)6][BF4]2 (M
= Co, Zn) in MeCN, slow evaporation of the reaction mixture
gave crystalline material with formula {[Co(H2O)2(MeCN)2(347)][BF4]4(MeCN)2(H2O)2}x in yields
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Scheme 131. (a) Formation of CB[6]-Based [2]Pseudorotaxane 344 and Its Self-Assembling 1D or 2D Coordination Polymers
345 and 346
Figure 57. (a) Formation of and (b) X-ray crystal structures of 1D, 2D, and 3D networks composed of DB24C8-based [2]pseudorotaxane subunits.
Reproduced with permission from refs 667 and 668. Copyright 2003 and 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Figure 58. (a) Chemical structure of [2]rotaxane 349 and (b) structure of MOFs by single-crystal X-ray diraction. Reproduced with permission
from ref 671. Copyright 2012 Nature Publishing Group.
geometry comprised four RL1 linkers in a square planar

arrangement, along with one water molecule and one
coordinated BF4 anion.
To aord 3D rotaxane-modied MOFs based on this system,
the dipyridinium ligand 348 containing bis(N-oxide) analogue
was designed and larger lanthanide metal ions were employed
(Figure 57).668 Thus, 3D MOFs with formula {[M(H2O)(OTf)(RL3)3][Cl][OTf]7(2MeCN)}x, (M = Sm, Eu, Gd, Tb)
were produced in moderate yield (50%). The use of Ln(III)
ions as nodes resulted in an eight-coordinate metal center with
a square anti-prismatic geometry comprised of six RL3 linkers,
one water molecule, and one coordinated triate anion. In this
3D structure (Figure 57), every linker is a [2]rotaxane, and the

edges of the cube are dened by SmSm distances of 23.5
. All of the rotaxane-modied MOF materials prepared above
showed the same basic stability. Thermogravimetric analysis
showed that all residual solvent was removed after heating to
100 C. Each MOF studied then showed a stable phase until
225250 C, at which point decomposition of the metal
ligand framework was indicated by loss of DB24C8.
Recently, a new approach to preparing three-dimensional
rotaxane-modied MOFs was described by Sessler.670 It relied
on the use of dicarboxylate anions threaded through a large,
tetracationic molecular box through a one-pot self-assembly
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Figure 59. Synthesis of [2]pseudorotaxane [350Cu]PF6 and MOF-1040. Reproduced with permission from ref 672. Copyright 2012 Wiley-VCH
Verlag GmbH & Co. KGaA, Weinheim.
Figure 60. (a) Single-crystal structure of MOF-1001 and the corresponding organic strut 351. (b) The cubic crystals of MOF-1001 and MOF-1001
pseudorotaxanes. Reproduced with permission from ref 673. Copyright 2009 American Association for the Advancement of Science.
crystals of MOF-1040 (Figure 59). Both oxidation and

demetalation experiments were demonstrated to occur without
disrupting the crystallinity of the frameworks, which indicated
the presence of electronic switches that were presumably
accompanied by geometrical changes involving shrinking and
attening in the coordination sphere of the copper ions in the
MOFs. They mark a signicant step toward transferring the
solution-state chemistry of MIMs into the solid state in the
form of a porous extended structure.
A typical example for application of rotaxane-modied MOFs
was presented by Stoddart, Yaghi, and co-workers.673 A electron-rich crown ether, capable of binding -electrondecient substrates, has already been introduced into MOFs.
MOF-1001 was capable of docking paraquat dication (PQT2+)
guests within the macrocycles in a stereoelectronically
controlled fashion (Figure 60). This act of specic complexation yielded quantitatively the corresponding MOF-1001
pseudorotaxanes, as conrmed by X-ray diraction and solidand solution-state NMR spectroscopic studies performed on
MOF-1001, its pseudorotaxanes, and their molecular strut
precursors. A control experiment involving the attempted
inclusion of PQT2+ inside a framework (MOF-177) devoid of
polyether struts showed negligible uptake of PQT2+, indicating
the importance of the macrocyclic polyether in PQT2+ docking.
process involving Zn(II) cations. Such a system represents

important progress toward controlling the features of 3D
MOFs.
In the above examples, rotaxane-modied MOFs were
constructed, in which the dumbbell components of rotaxanes
were used as struts in the framework and incorporated into
MOFs. It is still a challenge to accomplish motion of
components in the framework, or to locate switchable rotaxanes
inside extended frameworks.102,671 Recently, Loeb and coworkers constructed a MOF material using a [2]rotaxane 349
as the organic linker and binuclear Cu(II) units as the nodes
(Figure 58).671 Activation of the as-synthesized material created
a void space inside the rigid framework that allowed the soft
macrocyclic ring of the [2]rotaxane to rotate rapidly,
unimpeded by neighboring molecular components. The linker
was designed with two 3,5-benzenedicarboxylic acid groups as
the linking struts, a benzylaniline recognition site as the
crossbar, and a 24C6 macrocycle as the wheel. The Cu(II)based MOF [Cu2(349)(H2O)2]3H2O was prepared by
combining Cu(NO3)23H2O and the tetracarboxylate linker
349 in a 3:2:2 mixture of dimethylformamide (DMF)/EtOH/
H2O with trace HNO3. Variable-temperature 13C and 2H solidstate NMR experiments were used to characterize the nature
and rate of the dynamic processes occurring inside this unique
material. These results provide a blueprint for the future
creation of solid-state molecular switches and molecular
machines based on rotaxanes.
Stoddart, Yaghi, and co-workers reported the successful
incorporation of copper(I)-complexed [2]pseudorotaxanate
struts into a MOF.672 Mixing [2]pseudorotaxane [350Cu]
PF6 and Zn(NO3)26H2O in diethylformamide at 100 C in a
sealed tube for 48 h resulted in the formation of red cubic
6. CONCLUSIONS AND FUTURE PERSPECTIVES

In this Review, the development of pseudorotaxanes and
rotaxanes was introduced comprehensively in the order of their
historical sequence. We discussed trends in detail from
synthesis to stimuli-responsive movement in solution and
then in the solid supports, and to their function and
applications in molecular devices and materials science. In
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Biographies
their early stage of the development, investigations were

focused on the noncovalent interactions as synthetic templates,
mild reaction conditions for accomplishment of the template
synthesis without disrupting their interactions, matched
macrocyclic host and linear guest compounds as building
blocks, and sometimes appropriate bulky moieties as
stoppers.674,675 All in all, we provided a plentiful library for
the construction of more complicated supramolecular architectures and the development of molecular machines.
Given the unique structures and stimuli-responsive motional
properties of pseudorotaxanes and rotaxanes, they are
considered as ideal building blocks to obtain articial
nanomachines in solution. The association and dissociation
movement of pseudorotaxanes makes them good candidates for
achievement of the function of molecular locks and keys,
molecular switches, and molecular logic gates. Furthermore, the
shuttling or rotation of the wheel along the axle for rotaxanes
provides good opportunities for them to constitute molecular
machines, such as molecular shuttles, molecular switches, and
molecular abacus. There are still more complicated articial
molecular machines that are being continuously explored.676678
The eorts and studies of molecular machines based on
pseudorotaxanes and rotaxanes in solution are the basis for
understanding motional mechanisms and structurefunction
relationships for producing articial molecular machines in the
macroscopic world. Chemists have started their research on
these molecular machines in solid supports, such as in the solid
state, on surfaces, or in MOFs, which enable the functions of
nanovalves, ion sensing, single-molecular imaging, and catalysis
for the macroscopic systems. Therefore, the applications of
rotaxane-based molecular machines have attracted much
attention from biologists, materials and surface scientists,
polymer scientists, and so on. Up to now, studies on the
construction of drug delivery and release systems, stimuliresponsive supramolecular polymeric materials, and unidirectional charge-transfer cascades have been widely explored and
developed rapidly. However, this is just the beginning of a long
but exciting journey. For the purpose of constructing
macroscopic molecular machines, a lot of diculties still exist.
For example, how does one control exactly the molecular
motion of rings when these molecules are deposited on
surfaces? It is a challenging but indispensable problem that has
to be solved. Moreover, some new aspects have been involved
for the development of rotaxanes. Small rotaxane-based
molecular machines can be designed and operated to perform
their tasks in synthesis, such as the preparation of sequencespecic peptide.679 Another intriguing prospect of preparing
rotaxanes and the molecular switches is to amplify the
molecular switch process into mechanical work within liquidcrystalline properties. Some pioneering studies based on liquidcrystalline rotaxanes have been already reported and demonstrated their mesomorphic features.680,681 It seems that a vast
application eld is ready for development using such linear
interlocked molecules.
Min Xue was born in China in 1982. She obtained her B.S. in applied
chemistry from Xian Jiaotong University in 2005. She then got her
Ph.D. in chemistry from the Institute of Chemistry of the Chinese
Academy of Sciences under the supervision of Prof. Chuan-Feng Chen
in 2010. After that she moved to the group of Prof. Javier de Mendoza
at the Institute of Chemical Research of Catalonia (ICIQ) in Spain as
a postdoctor. In 2011, she joined the laboratory of Prof. Feihe Huang
at Zhejiang University as a postdoctor. Her current research interests
are the synthesis and assembly of pillararenes, molecular recognition,
and hostguest chemistry.
Yong Yang was born in China in 1979. He obtained his B.S. in

chemistry from Hunan University in 2002. He then joined Prof.
Chuan-Feng Chens group at the Institute of Chemistry of the Chinese
Academy of Sciences (ICCAS) to pursue his Ph.D. After obtaining his
Ph.D. in 2007, he continued his research at ICCAS as a research
assistant professor. In 2009 he moved to Prof. Javier de Mendozas
group at the Institute of Chemical Research of Catalonia (ICIQ) in
AUTHOR INFORMATION
Tarragona (Spain) as a postdoctor. Since 2011 he works as an
Corresponding Author
*E-mail: fhuang@zju.edu.cn.
independent PI at Zhejiang Sci-Tech University. His current interest is
Notes
the development and functionalization of hydrogen-bonding mediated
The authors declare no competing nancial interest.
self-assembly systems.
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Feihe Huang was born in China in 1973. He obtained his degree of

Doctor of Philosophy in Chemistry from Virginia Polytechnic Institute
and State University (VT) under the guidance of Prof. Harry W.
Gibson in March 2005. He then joined Prof. Peter J. Stangs group at
the University of Utah as a postdoctor. He became a Professor of
Chemistry at Zhejiang University in December 2005. His current
research interests are supramolecular polymers and pillararene
supramolecular chemistry. Awards he has received include the 2004
Chinese Government Award for Outstanding Self-Financed Students
Abroad, the Outstanding Ph.D. Dissertation Award from VT, the
Thieme Chemistry Journals Award, Humboldt Fellowship for
Experienced Researchers from the Humboldt Foundation, Fellow of
the Royal Society of Chemistry, Chinese Chemical Society AkzoNobel
Chemical Sciences Award, and Cram Lehn Pedersen Prize in
Supramolecular Chemistry. He has published more than 160
supramolecular chemistry papers. His publications have been cited
more than 8000 times with an h-index of 49. He has served as a guest
editor for Chemical Society Reviews, Accounts of Chemical Research,
Chemical Reviews, and Chemical Communications. He sits on the
Advisory Boards of Chemical Society Reviews, Chemical Communications,
Acta Chimica Sinica, Macromolecules, ACS Macro Letters, and Polymer
Chemistry.
Xiaodong Chi was born in Taizhou, Zhejiang, China on July 5, 1987.

He obtained his Bachelors degree in chemistry from Zhejiang SciTech University in June 2010. He then joined the group of Prof. Feihe
Huang at Zhejiang University to pursue his Ph.D. degree in chemistry.
His current research interests are the design and preparation of novel
hostguest recognition systems based on pillar[n]arenes, self-assembly
in aqueous media based on hostguest molecular recognition, and
functional supramolecular materials constructed by the combination of
traditional polymers and nonconvalent interactions.
supervision of Prof. Xuming Zheng in 2009. He then joined the
ACKNOWLEDGMENTS
We greatly acknowledge the National Basic Research Program
(2013CB834502), the National Natural Science Foundation of
China (21125417, 21202145, 21434005), the Fundamental
Research Funds for the Central Universities, the Key
Laboratory of Supramolecular Structure and Materials, and
the China Postdoctoral Science Foundation (2013M541767)
for their generous nancial support. F.H. is very grateful to
Professor Harry W. Gibson for his enormous support and
encouragement.
laboratory of Prof. Feihe Huang at Zhejiang University and obtained
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Review

Development of Pseudorotaxanes and Rotaxanes: From Synthesis to

2015 American Chemical Society

Special Issue: 2015 Supramolecular Chemistry

Furthermore, the most popular and eective click chemistry

Figure 1. Cartoon representations of pseudorotaxane, semirotaxane,

The strategies for the synthesis of rotaxanes developed from

Scheme 1. First Synthesis of a [2]Rotaxane by the Statistical Threading Method

Scheme 2. General Approaches to the Construction of

Figure 2. Cartoon representations of dierent types of rotaxanes.

Up to now, rotaxane-based chemistry has been developed to

capping the thread with bulky groups to prevent it from

2. SYNTHESIS OF ROTAXANES BASED ON VARIOUS

followed-by-shrinking strategy,56,57 the free space within the

Scheme 3. New Strategies for the Construction of Rotaxanes

Figure 3. Macrocycles used in the synthesis of rotaxanes.

the early plentiful work, crown ethers have become very

and rotaxanes can be divided into hydrogen bonding,

Crown ethers, which were rst discovered by Charles Pedersen

heterophilic recognition nature (Scheme 4).77 Complexation of

garnering any signicant [CHO] interactions with 88+.

Scheme 6. Self-Sorting Organization of Heteroditopic Monomers 9 and 10a

based on the DB24C8/dibenzylammonium cation recognition

the dierent binding abilities of DB24C8 and BPP34C10. It led

Scheme 7. Formation of Cyclophane-Modied DB24C8-Based [2]Rotaxane 165TFA

Figure 4. Formation of [2]rotaxanes based on the DB24C8/BPE recognition motif.

crown-8 type wheels were constructed with either symmetrical

Scheme 9. Synthesis of [2]Rotaxane 25 via Aminolysis of

an amine having a bulky group in C6H6 gave [2]rotaxane 25 in

Scheme 10. Solid-State Synthesis of [4]Rotaxane 29-H33PF6a

phenyl groups as the stoppers was successfully prepared in 74%

Scheme 11. Synthetic Route to and X-ray Crystal Structure

Scheme 13. Formation of Sequence-Specic Hetero[3]rotaxane 382PF6

workers designed and prepared a series of cryptands based on

conditions, while DB24C8 thermodynamically preferred 33PF6

Figure 5. Chemical structures of BMP32C10-based cryptands and their guests.

Scheme 16. Synthesis of Cryptand-Based [2]Rotaxanes 582PF6 and 603PF6

cryptand 39a and paraquat in the solid state.131 On the other

stoichiometry do exist, which was evidenced by the crystal

[3]pseudorotaxane with cryptand 39a, and the complexation

Figure 6. Chemical structures of triptycene-derived crown ether hosts

designed and synthesized, which showed good binding ability

Cyclodextrins (CDs) are a series of cyclic oligosaccharides

formation of CD-based rotaxanes.155158 In 1981, Ogino and

Figure 7. (a) Chemical structure of -CD, and (b) the cartoon

unique complexation ability in aqueous solution mainly through

[3]rotaxane -CD(68)2 and hetero-[3]rotaxane -CD(68

Scheme 18. Synthesis of -CD-Based [3]Rotaxane CD(6870)

substantial cavity and then acted as a host to bind another

Scheme 20. Synthesis of the Size-Complementary -CD-Based Rotaxanes

Scheme 21. Synthesis of the Carbohydrate Linked -CD-Based Rotaxanes

21).185 The preparation of such interlocked molecules involved

molecular polymers represent a large family, which is not

Cucurbit[n]urils (CB[n]s), each of which consists of n

Figure 8. Structure and cartoon representation of CB[n].

contruction of pseudorotaxanes and rotaxanes. The initial

Figure 9. Pseudorotaxane-terminated dendrimer. Reproduced with

Scheme 22. Synthesis of [2]Rotaxane 88 Based on the CB[6]/Spermine Recognition Motif

Scheme 25. Synthesis of CB[7]-Based [2]Rotaxane 94