Laboratory Experiment

pubs.acs.org/jchemeduc

Fluorescence Aggregation-Caused Quenching versus Aggregation-

Induced Emission: A Visual Teaching Technology for Undergraduate
Chemistry Students
Xiaofeng Ma, Rui Sun, Jinghui Cheng, Jiaoyan Liu, Fei Gou, Haifeng Xiang,* and Xiangge Zhou*
College of Chemistry, Sichuan University, Chengdu 610041, China
*
S Supporting Information

ABSTRACT: A laboratory experiment visually exploring two

opposite basic principles of fluorescence of aggregation-caused
quenching (ACQ) and aggregation-induced emission (AIE) is
demonstrated. The students would prepared two salicylalde-
hyde-based Schiff bases through a simple one-pot condensa-
tion reaction of one equiv of 1,2-diamine with 2 equiv of
salicylaldehyde. The resulting fluorescent dyes have similar
chemical structures but possess ACQ and AIE properties,
respectively. Their ACQ/AIE properties and pH sensing
applications would then examined by visually qualitative analysis (UV lamp, light-emitting diode, and naked eye) and quantitative
analysis (fluorometer). Finally, in a deeper level, X-ray single crystal structure analysis was utilized to reveal the inherent
relationships between molecular structures/molecular arrangements and ACQ/AIE properties. This lesson is suitable for many
areas of chemistry, especially for organic and analytical chemistry.
KEYWORDS: Upper-Division Undergraduate, Analytical Chemistry, Organic Chemistry, Fluorescence Spectroscopy,
X-ray Crystallography, Hands-On Learning/Manipulatives, Aldehydes/Ketones, pH, Solid State Chemistry, Solutions/Solvents

■ INTRODUCTION
Luminescence (fluorescence or phosphorescence), which is
challenging for organic light-emitting diodes (OLEDs) and
light-emitting electrochemical cells applications,15 where the
spontaneous light emission coming from excited electronic luminophores are in solid state and might have a more severe
states after absorption of UV/visible light, has received great ACQ effect.
attention in many disciplines, such as chemistry, physics, Tang and co-workers recently discovered an exactly opposite
material science, medicine, and biology.1−4 Among numerous phenomenon to the notorious ACQ effect. 1-Methyl-1,2,3,4,5-
works2−13 demonstrating the basic principles of fluorescence or pentaphenylsilole molecule (Figure 1) had no fluorescence in a
phosphorescence in this Journal, the photophysical properties
including absorption and emission spectra,2 luminescence
decay lifetime5 and quantum yield (Φ),6 emission quenching,7
and sensing applications8−11 of organic luminescent materials
are generally studied in dilute solution. In these conditions, it is
thought that there are no intermolecular interactions between
the isolated organic molecules in dilute solution. However,
many organic materials in dilute solution exhibit very different
photophysical properties compared with in concentrated
solution. For example, it is a common phenomenon that
luminescence is often weakened or quenched at high
concentrations. This “concentration quenching” is mainly
caused by the “formation of aggregates”, which has frequently
been referred to as “aggregation-caused quenching” (ACQ).14
It should be noted that the ACQ effect is harmful to some
practical applications. For example, the preferred work Figure 1. Chemical structure of AIE-active 1-methyl-1,2,3,4,5-
conditions for detection applications are water, but most pentaphenylsilole.
organic luminescence probes are hydrophobic aromatics and
cannot be dissolved in water. Therefore, they are liable to Received: February 18, 2015
precipitate and aggregate in water, resulting in ACQ effect. Revised: November 12, 2015
Moreover, the ACQ effect might be more harmful and Published: December 18, 2015
© 2015 American Chemical Society and
Division of Chemical Education, Inc. 345 DOI: 10.1021/acs.jchemed.5b00483
J. Chem. Educ. 2016, 93, 345−350
Journal of Chemical Education Laboratory Experiment

dilute ethanol solution. In concentrated solutions or solid films, use fluorescence spectroscopy and hand-held UV light to
however, its fluorescence became very strong.16 In dilute examine AIE/ACQ phenomenon. The experimental data would
organic solution, its five phenyl rotors undergo dynamic be processed by software, such as Microsoft Excel and Origin.
intramolecular rotations (IRs), which provides a possible way Owing to the time limit of class, the parts of pH sensing
to nonradiatively annihilate its excited states and results in the application and molecular structures/molecular arrangements
absence of luminescence. Nonetheless, in the aggregates, can be demonstrated by teacher.
molecules are tightly packed, which would eliminate these The experiment has been performed by two groups. One is a
IRs. Furthermore, silole molecules cannot pack through face-to- senior-class organic chemistry group (8 students), the other is a
face π−π interactions due to its propeller shape (Figure 1). senior-class analytical chemistry group (10 students). For an 8-
This restriction of both IRs and π−π interactions would help to h 1 day experiment, during the morning, students would finish
turn off the nonradiative transitions and turn on the radiative two reactions within 4 h and then purify the dyes by
pathways. Thereby, the silole molecules become emissive in the recrystallization from ethanol in the refrigerator during lunch
aggregate state. The authors termed the process “aggregation- time. The chemical reactions are very quick and complete. As
induced emission” (AIE). After that, the AIE-active materials determined by thin-layer chromatography, the reactions are
have been an area of topical interest in a number of research complete within 1 h with almost 100% yields. During the
areas, including OLEDs, luminescence probes, and bioimag- afternoon, students use approximately half an hour to isolate
ing.17,18 and dry the dyes by filtration. Then, students examine their
Although a lot of classroom experiments on fluorescence and ACQ/AIE properties by visually qualitative analysis (UV lamp,
phosphorescence have been present for decades,2−13 to the best
LED, and naked eye) and quantitative analysis (fluorometer)
of our knowledge, none entails the synthesis and study of
within 3 h. In the remainder (half an hour) of the class period,
ACQ/AIE-active fluorophores. This classroom experiment
the teacher demonstrates the pH sensing application and
describes a visual teaching lesson, ACQ vs AIE, in which
molecular structures/molecular arrangements and summarizes
undergraduate chemistry students are exposed to the
magnificent world of luminescence. Students would prepare the experiment. After the experiment, students process data and
one ACQ-active (SB1)19,20 and one AIE-active (SB2)21,22 write experimental reports. If laboratories are not going to have
Schiff base (Figure 2) by a simple one-pot condensation of the opportunity for undergraduates to spend 8 h in 1 day in the
laboratory, the experiment can be performed in two half days,
just like morning and afternoon portions of the 8-h 1 day
experiment.

■ EXPERIMENTAL DETAILS
Materials and Instrumentation

Figure 2. Chemical structures of SB1 and SB2.

All reagents and organic solvents were purchased from
commercial suppliers and used without further purification.
UV/visible absorption spectra were recorded using a UV 765
diamine with 2 equiv of salicylaldehyde and then try to examine spectrophotometer (Shanghai Precision & Scientific Instru-
their ACQ/AIE properties and pH sensing applications. ment). Fluorescence spectra were obtained using an F-7000
Moreover, if students were interested in the inherent Fluorescence spectrophotometer (Hitachi). A hand-held UV
relationships between molecular structures/molecular arrange- lamp (360 nm) or UV LED (385 nm) was used as light source
ments and ACQ/AIE properties of these two similar Schiff to excite fluorescence for visual demonstrations. The synthetic
bases, they could obtain more information from the X-ray procedures and fluorescence analysis methods of SB1 and SB2
single crystal structure analyses. were described in the Supporting Information.

■ EXPERIMENTAL OVERVIEW
This experiment is 1 day (8 h) class. During the experiment,
Synthesis of SB1
4-(Diethylamino)salicylaldehyde (2.1 mmol, 0.41 g) was added
students would prepare, purify, and characterize ACQ/AIE 100 mL of absolute ethanol of diaminomaleonitrile (1.0 mmol,
properties of organic dye SB1 and SB2. SB1 and SB2 can be 0.11 g). After adding one drop of sulfuric acid as a catalyst, the
synthesized in a straightforward way with high yields (Figure mixture was stirred and refluxed for 2 h to give a dark green
3). The reactions can be done in air. Water-free and oxygen- precipitate. The precipitate was filtered and then recrystallized
free conditions are unnecessary. Purifications can be ready to from ethanol (∼50 mL) in the refrigerator to give a dark green
accomplish by recrystallization and filtration. Students would solid. After suction filtering, ethanol washing (20 mL), and air
drying, 0.34 g dark green solid was obtained (74% yield).
Synthesis of SB2
Absolute ethanol (30 mL) with aqueous hydrazine (5 mmol,
0.25 g) was dropwise added into 20 mL absolute ethanol of
salicylaldehyde (10 mmol, 1.22 g) in a period of 1 h. Then, the
mixture was refluxed for 2 h to give crude yellow precipitate.
The precipitate was filtered and then recrystallized from
ethanol (∼50 mL) in refrigerator to give a yellow solid. After
suction filtering, ethanol washing (20 mL), and air drying, 0.92
Figure 3. General methods for the preparation of SB1 and SB2. g pale yellow solid was obtained (77% yield).
346 DOI: 10.1021/acs.jchemed.5b00483
J. Chem. Educ. 2016, 93, 345−350
Journal of Chemical Education Laboratory Experiment

Figure 4. Pictures (top, under room light; bottom, under 360 nm UV light) of (left) SB1 in MeCN/water (1.0 × 10−6 mol/L) with different f values
and (right) solid SB1.

Figure 5. Pictures (top, under room light; bottom, under 360 nm UV light) of (left) SB2 in MeCN/water (1.0 × 10−5 mol/L) with different f values
and (right) solid SB2.

Fluorescence Analysis the dilute solution of MeCN (1.0 × 10−6 mol/L), SB1
The concentration of SB1 and SB2 in MeCN was 1.0 × 10−6 functionalizing a donor−acceptor (DA) systems is liable to
and 1.0 × 10−5 mol/L, respectively. The aggregated SB1 and produce intramolecular charge transfer from the electron-
SB2 in MeCN/water were prepared by adding the high- donating substituent of NEt2 to the central electron-
concentration dye into water (Supporting Information). accepting fragment of CN, resulting in its low-energy
Fluorescence spectra were obtained using an F-7000 absorption band (λabs = 564 nm) and red emission (λem =
Fluorescence spectrophotometer (Hitachi) at room temper- 606 nm) with an unexpectedly high Φ up to 0.80. However, if
ature. Furthermore, a hand-held UV light (360 nm) or LED water is added into the MeCN solution of SB1, the
(385 nm) was used to excite these solution samples for a visual fluorescence recedes (Figures 4 and S2), because SB1 cannot
demonstration.

■
be dissolve in water, which causes SB1 molecules to precipitate
and aggregate. When the volume fraction ( f) of water is
HAZARDS increased to 70%, the fraction of MeCN is too low to dissolve
For the purpose of safety, students should wear nitrile gloves SB1, resulting in that most of the SB1 molecules are in the
and goggles at ALL TIMES during the experiment. Chemical form of aggregation. Consequently, the aggregation would
reactions should be handled in fume hoods. The dyes might be quenched the fluorescence of SB1 completely. This ACQ
cancer suspect agents. Caution: Do not directly touch with nature of SB1 in water or solid state even can be visible to a
hand; in case of contact, rinse directly. Because aldehyde and
naked eye (Figures 4 and S3).
amine are toxic, they touching the skin should be avoided.
MeCN and EtOH are flammable. High-energy UV light is Photophysical and AIE Properties of SB2
harmful to the skin and eyes. Unnecessary exposure of skin and The photophysical properties of SB2 were also systematically
eyes to UV light is not allowed. examined by the previous report.22 The UV/visible absorption

■ RESULTS AND DISCUSSION

Synthesis of the ACQ/AIE-Active Dyes
and emission spectral data of SB2 are listed in Table S1 as well.
Contrary to SB1, SB2 in the dilute solution of MeCN (1.0 ×
10−5 mol/L) exhibits very weak emission (λem = 509 nm) with
As shown in Figure 3, both SB1 and SB2 can be simply and an ultralow Φ of 0.002 (Figure S4). Nonetheless, its
efficiently prepared by a one-pot condensation reaction of 1 fluorescence is strengthened if water is added into MeCN
equiv of diamine with 2 equiv of salicylaldehyde in ethanol (Figures 5, S5, and S6) due to the formation of aggregation.
under reflux, according to the previous reports.19,22 Both SB1 When f of water is increased to 92%, its fluorescence attains the
and SB2 have good solubility in organic solvents, such as maximum (Φ = 0.11). The previous work19 also demonstrated
DMSO and MeCN, but they have poor solubility in water or that SB2 molecules would form nanoparticles (<5 nm) when
hexane. Both SB1 and SB2 are stable in solid and solution for water was added, which indicates SB2 molecules are dispersed
characterization and application. but not dissolved in water. Unlike SB1 (Figure 4), SB2 in solid
Photophysical and ACQ Properties of SB1 state emits strong yellow-green emission under 360 nm UV
The photophysical properties of SB1 were systematically lamp (Figure 5). All of the aforementioned findings confirm
examined by the previous reports.19,20,23 The UV/visible that SB1 and SB2 own totally opposite ACQ and AIE
absorption and emission spectral data of SB1 are listed in properties, respectively, in spite of their similar chemical
Table S1 (Supporting Information). As shown in Figure S1, in structures.
347 DOI: 10.1021/acs.jchemed.5b00483
J. Chem. Educ. 2016, 93, 345−350
Journal of Chemical Education Laboratory Experiment

Fluorescent pH Sensing Applications of SB1 and SB2 efficiently prevent two phenolic rings from IRs and non-
The fluorescent pH sensing applications of SB1 and SB220 22 radiative annihilations. Therefore, SB1 are highly emissive in
were reported previously. Because of the time limit of lesson, dilute organic solvent (Figure 7).
this part can be demonstrated by teacher. The teacher should
emphasize the fact that SB2 might be better than SB1 for
sensing applications because SB2 is highly emissive in water
due to its nature of AIE, but the ACQ nature of SB1 would be
harmful for the detection in the media of water, and thus, SB1
must be used in the media of organic solvent. As shown in
Figure S7, the emission properties of SB2 are strongly
dependent on pH values. The mixed solvents of MeCN/
aqueous Britton−Robinson (B−R) buffer solution (SB2 1.0 ×
10−5 mol/L in MeCN/water, f = 92%) were adopted for
fluorescent pH sensing applications. The fluorescence intensity
of SB2 at 536 nm (I536) remains unchanged when pH < 8.0, but
it weakens when pH values increase from 8.0 to 11.0 and finally
remains unchanged again when pH > 11.0, indicating that its
pKa is 9.3. At the same time, I513 belonging to the deprotonated Figure 7. Schematic diagram of fluorescence mechanism for SB1
SB2 has a totally adverse pH response (which is zero), molecule.
increased, and was constant at pHs of <8.0, 8.0−11.0, >11.0,
respectively. Moreover, SB2 provides a perceived color change In the aggregates, however, the disc-like SB1 molecules are
for rapid visual sensing (Figure 6). It is known that phenol is a face-to-face stacking (Figure S9a) with a very short interplanar
distance (d) of ∼3.05 Å (Figure S9b), resulting in very strong
face-to-face π−π interactions between two neighbor SB1
molecules. These π−π interactions might be expressed directly
by the overlaps in two π-conjugated systems (Figure S9b and
S9c) and would facilitate the formation of excimers, which lead
to emission quenching and ACQ effect thereby (Figure 7).18,22
Therefore, if one wants to design luminescent materials for
some applications in dilute solution, big π-conjugated system
and less IRs are primary factors to consider.
Molecular Structures/Molecular Arrangements of SB2
As shown in Figure S10, all atoms in the SB2 molecule are
Figure 6. Pictures (top, under room light; bottom, under 360 nm UV almost located in one plane of π-conjugated system of SB2. As
light) of SB2 (1.0 × 10−5 mol/L in MeCN/water, f = 92%) in B−R expected, the similar intramolecular hydrogen bonds (1.90 Å)
buffer solution at different pH values. are also observed in SB2, like SB1. However, it is obvious that
there are still N−N single bond IRs in SB2 molecules, which
weak acid (pKa = 10).24 SB2 (pKa = 9.3) containing electron- would be contributed to the absence of luminescence for SB2
accepting salicylaldimine moiety is more acid than phenol. The in the dilute solution of MeCN (Figure 8).
electron density of a benzene ring would be decreased by the
inductive effect of electron-accepting substituent, which would
delocalize the negative charge of phenolic hydroxyl into the
benzene ring. And then, the resultant phenolate anion has a
better stability to release the proton of phenolic hydroxyl,
resulting in the fact that the acidity of SB2 is bigger than that of
phenol.22
Molecular Structures/Molecular Arrangements of SB1
Because the molecule structures and arrangements play an
important role in ACQ or AIE effect, the X-ray single crystal
analysis are carried out by a crystal and molecular structure
visualization software, such as Diamond 3.2.25 The X-ray
structures of SB126 and SB227 were previously reported and
their crystallographic information files (CIF) are available via Figure 8. Schematic diagram of fluorescence mechanism for SB2
the Internet. Owing to the time limit of lesson, this part can be molecule.
demonstrated by teacher as well.
As shown in X-ray single crystal structures of SB1 (Figure In the aggregates, the cross-stacking (Figure S11a) SB2
S8), except the carbon and hydrogen atoms in two NEt2 molecules have a short d of ∼3.45 Å (Figure S11b). Although
groups, all other atoms in SB1 are almost located in one big this d value is a bit longer than that of SB1 (∼3.05 Å), it is
plane of π-conjugated system of SB1, which provides an short enough for SB2 molecules to pack tightly to eliminate
efficient way to absorb the excitation energy from UV/visible NN single bond IRs and achieve AIE subsequently. Anyway,
light. Moreover, the intramolecular hydrogen bonds (1.94 Å) it is noteworthy that some intermolecular face-to-face π−π
(−OH···N) are observed in SB1. These hydrogen bonds would interactions between two neighbor SB2 molecules are still
348 DOI: 10.1021/acs.jchemed.5b00483
J. Chem. Educ. 2016, 93, 345−350
Journal of Chemical Education

■
Laboratory Experiment

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350 DOI: 10.1021/acs.jchemed.5b00483

J. Chem. Educ. 2016, 93, 345−350