Published on Web 07/06/2009

Synthesis and Spectroscopic Studies on Azo-Dye Derivatives of Polymetallic

Lanthanide Complexes: Using Diazotization to Link Metal Complexes
Together
Matteo P. Placidi,† Aaron Joseph L. Villaraza,† Louise S. Natrajan,† Daniel Sykes,†,‡
Alan M. Kenwright,§ and Stephen Faulkner*,†,‡
School of Chemistry, UniVersity of Manchester, Oxford Road, Manchester M13 9PL, U.K., UniVersity of Oxford,
Chemistry Research Laboratory, 12 Mansfield Road, Oxford OX1 3TA, U.K., and Department of Chemistry,
UniVersity of Durham, South Road, Durham DH1 3LE, U.K.
Received May 29, 2009; E-mail: Stephen.Faulkner@chem.ox.ac.uk

Lanthanide complexes have been widely used in a variety of Scheme 1. Synthesis and Diazotization of Phenol Bridged
imaging and assay related applications. In particular, gadolinium Bis-Macrocycles and Their Complexesa
complexes have been used as contrast agents in magnetic resonance
imaging,1 while luminescent lanthanide ions are widely used in
bioassay2 and imaging.3 In such applications, it is important to be
able to control the local environment around the metal and form
kinetically stable complexes.4 For instance, in magnetic resonance
imaging a complex should allow close approach and rapid exchange
of water molecules, while retaining sufficient kinetic stability to
be excreted intact. The case is altered for luminescence applications,
since the excited states of lanthanide ions are quenched nonradia-
tively by vibrational harmonics of the O-H oscillator and it is
therefore desirable to exclude water molecules from the inner
sphere.5 Since electric dipole f-f transitions are Laporte forbidden
and have very low extinction coefficients, sensitizing chromophores
are often incorporated into the ligand structure: these can sensitize
emission from the lanthanide excited state and lead to dramatic
enhancement of the emission from the metal center.6 Energy transfer
from the chromophore to the metal is usually mediated via the
chromophore triplet state,7 though other mechanisms have also been
shown to be viable in some complexes.8,9
Kinetically stable complexes can also be used as building blocks
for more complicated systems10 and can even be used in the
preparation of heterometallic lanthanide complexes containing
different lanthanide ions.11 a
Reagents and Conditions: (a) Cs2CO3, MeCN reflux, 72 h; (b) tfa,
We now report how related bimetallic complexes can be linked CH2Cl2, 48 h; (c) Ln(OTf)3, MeOH, 50 °C, 48 h; (d) 4-nitroaniline, NaNO2,
together using diazotization reactions that generate a chromophore HCl, 0 °C, 0.5 h.
at the heart of the assembly, permitting visible light excitation of
the bound lanthanide ions. As expected, azo dye formation results in a color change: the
[Ln2.4]- complexes are colorless, while [Ln2.5]- complexes are
The synthesis of phenolic complexes suitable for reaction with
deep red, owing to the increased conjugation between the phenolic
diazonium salts is outlined in Scheme 1. Reaction of the well-known
oxygen donor and the nitro group acceptor.
DO3A derivative12 (1) with 2-6-bis(bromomethyl)phenoxy acetate
All the complexes were found to be emissive in the near-IR
(2) in the presence of cesium carbonate followed by aqueous
region of the spectrum, and data fitted well to single exponential
workup yielded 3. NMR revealed that cleavage of the phenoxy
decays, suggesting that the conformers of the complex are in fast
acetate ester had occurred under the reaction conditions, obviating
exchange on the luminescence time scale, unlike the case of an
the need for its subsequent removal.
analogous complex with a 4-methyl substituent on the phenol
Cleavage of the tert-butyl esters in trifluoroacetic acid unmasked bridge, for which double exponential behavior has been observed.13
both lanthanide binding sites, and treatment with lanthanide triflate Time resolved luminescence spectroscopy was used to establish
salts resulted in the formation of bimetallic complexes [Ln2.4]- the luminescence lifetimes of the complexes, and the number of
(Ln ) Nd, Yb). Reaction of [Ln2.4]- with a 4-nitrophenyl diazo- inner sphere water molecules in the ytterbium complexes was
nium salt in aqueous solution resulted in the formation of azo dyes determined from the luminescence decay constants in H2O and D2O
[Ln2.5]- (Ln ) Nd, Yb). These were purified using size selective using the formula
dialysis tubing to separate any unreacted [Ln2.4]- from the product.
q ) 1.0(kH2O - kD2O - 0.1)
†
University of Manchester. where q is the number of bound water molecules at each ytterbium
‡
University of Oxford.
§
University of Durham. ion, and kH2O and kD2O are the observed rate constants in H2O and
9916 9 J. AM. CHEM. SOC. 2009, 131, 9916–9917 10.1021/ja904362f CCC: $40.75  2009 American Chemical Society
 COMMUNICATIONS
-1 14
D2O, respectively (with units of µs ). No values were calculated conceivably as a result of steric crowding in the tetrametallic
based on neodymium luminescence owing to the large variations complex inhibiting access by solvent to the metal center; indeed
in lifetime with ligand structure in such systems.2 The photophysical qYb for Yb2.7 is the same as qYb for 9, while qYb for Yb2.5 is within
properties of the lanthanide complexes are shown in Table 1. error of that for 8.
Table 1. Photophysical Properties of the Complexesa

compound λem/nm τH2O/ns τD2O/ns qYb

Nd2.4 1055 98 301
Yb2.4 980 1620 4510 0.3
Nd2.5 1340 112 355
Yb2.5 980 1410 4020 0.4
Nd2.7 1055 102 334
Yb2.7 980 1600 5310 0.3
8 980 1950 5120 0.2
8 1340 140 320
9 980 1750 5170 0.3
Figure 1. Time-gated emission spectra of D2O solutions containing 8
9 1340 160 400
(dashed line) and 9 (solid line): (a) in the period between 500 and 1000 ns
a after the laser pulse; (b) from 3 to 6 µs after the laser pulse, normalized at
All complexes exhibited emission following excitation at 337 nm.
980 nm.
For [Ln.5]- and 8 and 9, excitation at 420 nm gave lifetimes within
error of those given in the table.
The stability of systems such as these in the forcing conditions
Having prepared and studied bimetallic systems, we turned our inherent to diazotization reactions is further evidence for the kinetic
attention to the preparation of heterotetrametallic arrays. Scheme inertness of such complexes. This approach allows not only the
2 shows the synthetic strategy employed. The bis-macrocycle 7 preparation of heterometallic systems containing different lanthanide
was prepared using an established procedure as shown in Scheme ions but also the simultaneous incorporation of a sensitizing
2.15 Complexation with the lanthanide triflate yielded the bimetallic chromophore.
complexes Ln2.7. Reaction of Ln2.7 with sodium nitrite in dilute
Acknowledgment. The authors acknowledge support from the
hydrochloric acid followed by addition of [Ln′2.4]- yielded the
Universities of Manchester, Oxford, and Durham and from the
tetrametallic complexes 8 and 9.
EPSRC.
Scheme 2. Synthesis of Tetrametallic Complexesa
Supporting Information Available: Experimental procedures and
characterization data for synthesis of compounds and complexes,
absorption and (time-resolved) emission spectra of complexes. This
material is available free of charge via the Internet at http://pubs.acs.org.

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