Aggregation-induced CPL response from chiral binaphthyl-based AIE-active polymers via supramolecular self-assembled helical nanowires

Article abstract of DOI:10.1016/j.polymer.2018.04.006

In this paper chiral polymer R-P could be synthesized by click polymerization reaction of (R)-3,3′-diethynyl-2,2′-bis(octyloxy)-1,1′-binaphthalene (R-M-1) and 1,2-bis(4-azidophenyl)-1,2-diphenylethene (M-2), and S-P was obtained by click polymerization re

Full text of DOI:10.1016/j.polymer.2018.04.006

Accepted Manuscript
Aggregation-induced CPL response from chiral binaphthyl-based AIE-active polymers
via supramolecular self-assembled helical nanowires
Jing Ma, Yuxiang Wang, Xiaojing Li, Lan Yang, Yiwu Quan, Yixiang Cheng
PII:
S0032-3861(18)30292-1
10.1016/j.polymer.2018.04.006
JPOL 20486
DOI:
Reference:
To appear in: Polymer
Received Date: 20 January 2018
Revised Date: 28 March 2018
Accepted Date: 2 April 2018
Please cite this article as: Ma J, Wang Y, Li X, Yang L, Quan Y, Cheng Y, Aggregation-induced CPL
response from chiral binaphthyl-based AIE-active polymers via supramolecular self-assembled helical
nanowires, Polymer (2018), doi: 10.1016/j.polymer.2018.04.006.
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Graphical Abstract
Aggregation-induced CPL Response from Chiral
Binaphthyl-based AIE-active Polymers via Supramolecular
Self-assembled Helical Nanowires
†
†
†
†
†,
Jing Ma, Yuxiang Wang, Xiaojing Li, Lan Yang, Yiwu Quan, * and Yixiang
Cheng †, *
†
Key Lab of Mesoscopic Chemistry of MOE, Collaborative Innovation Center of
Chemistry for Life Sciences, School of Chemistry and Chemical Engineering,
Nanjing University, Nanjing 210023, China
E-mail: yxcheng@nju.edu.cn; quanyiwu@nju.edu.cn
Chiral conjugated polymer enantiomers incorporating 1,1’-binaphythyl
and
tetraphenylethene (TPE) can exhibit strong CPL signals due to the formation of the
supramolecular self-assembled helical nanowires in the aggregate.

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Aggregation-induced CPL Response from Chiral
Binaphthyl-based AIE-active Polymers via Supramolecular
Self-assembled Helical Nanowires
†
†
†
†
†,
Jing Ma, Yuxiang Wang, Xiaojing Li, Lan Yang, Yiwu Quan, * and Yixiang
Cheng †, *
†
Key Lab of Mesoscopic Chemistry of MOE, Collaborative Innovation Center of
Chemistry for Life Sciences, School of Chemistry and Chemical Engineering,
Nanjing University, Nanjing 210023, China
E-mail: yxcheng@nju.edu.cn; quanyiwu@nju.edu.cn
Graphical Abstract
In this paper chiral polymer R-P could be synthesized by click polymerization reaction of
(R)-3,3’-diethynyl-2,2’-bis(octyloxy)-1,1’-binaphthalene
(R-M-1)
and
1,2-bis(4-azidophenyl)-1,2-diphenylethene (M-2), and S-P was obtained by click polymerization
reaction of (S)-3,3’-diethynyl-2,2’-bis(octyloxy)-1,1’-binaphthalene (S-M-1) and M-2,
respectively. R-/S-P enantiomers can show strong aggregation-induced circularly polarized
luminescence (AICPL) emission signals in the aggregate and cast-spin film, and the dissymmetry
factors (glum) can be up to 6.97 × 10-3 and 1.45 × 10-2, respectively. The SEM images further

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demonstrate that AICPL response behavior of R-/S-P can be attributed to the formation of the
supramolecular self-assembled helical nanowires in the aggregation state at 90% of the fraction of
water (fw).
Introduction:
In the past decades, more and more efforts have been devoted to the chiral conjugated polymers
since the polymer chain backbone with the delocalizable π-electronic structures and molecular
wire features can greatly amplify the fluorescence response signals through facile energy
migration along the polymer backbone upon the light excitations.[1] Currently, chiral conjugated
polymers have attracted increasing attentions on their optical functions,[2] especially circularly
polarized luminescence (CPL) materials, which can be regarded as the selective emission of left-
and right-handed polarized light. Normally, chiral feature signals (CD, CPL, and so on) can be
effectively amplified via the synergic effect between the conjugated polymer backbone structure
and chiral moiety.[3] Considering the potentially significant application of CPL materials, such as
biomedical diagnosis,[4] cell imaging[5] and catalysts for asymmetric photochemical synthesis,[6]
developing novel chiral conjugated polymers is of great importance.
In 2001 aggregation-induced emission (AIE) was firstly proposed by Tang, illustrating the
phenomenon that almost no luminescence can be observed in solution, but stronger emission
happened in aggregate or solid state.[7] Recently, there have been more and more reports on
AIE-active functional materials for chemosensors, biological imaging,[8] fluorescent probe[9] and
OLED devices.[10] Tang's group first reported a small molecule containing an AIE-active silole
core and chiral sugar pendants, which exhibited great glum value up to -0.12 and -0.08 in

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heterogeneous suspension and neat static cast film.[11] Recently, Liu’s group also found a general
approach for fabricating 1D aggregation-induced CPL (AICPL) nanoassemblies of
1,3,5-benzenetricarbonyl-based L-glutamate diethyl ester and styrylbenzene derivatives, which
successfully encapsulated guest achiral AIE dyes into the chiral space.[12] Although Tang’s group
reported some AICPL materials based on chiral AIE-active small molecules, so far there have
been very few works on AIE-active chiral conjugated polymers as AICPL materials.[13]
Chiral 1,1’-binaphthol (BINOL) have been widely used as the starting materials for the synthesis
of chiral conjugated polymers with main chain chiral configuration. These binaphthyl-based
polymers can exhibit efficient and stable chiral configuration as well as high chiral induction,
which represents a new generation of materials for asymmetric catalysis[14] and enantioselective
recognition.[15] Besides, click reactions, represented by the copper(I)-catalyzed azide-alkyne
cycloaddition (CuAAC), have been successfully employed to design various functional materials
due to their feasibility, selectivity, and high-yield,[16] especially involving in the fabrication of
biological materials[17] and chiral materials.[18] Our group first synthesized chiral conjugated
polybinaphthyls via click polymerization reaction, this kind of polymers containing a triazole
moiety in the polymer main chain backbone could show high sensitivity and selectivity for Hg2+
recognition.[19] Recently our group developed tunable green AICPL materials of three-component
chiral binaphthyl-based conjugated polymers via FRET mechanism from fluorene moiety to
AIE-active TPE chromophore.[13a] To our best knowledge, so far there has been no report on
AICPL material based on AIE-active chiral conjugated polymers via click polymerization reaction.
Herein, we designed and synthesized the novel AIE-active chiral binaphthyl-based polymer
enantiomers R-/S-P by using click polymerization reaction, and strong AICPL response behavior

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can be attributed to the formation of the supramolecular self-assembled helical nanowires in the
aggregation state. We believe that these AIE-active chiral conjugated polymers will be regarded as
one of the most promising candidate materials for CPL emitters on optical sensor, 3D display and
other photoelectric functional applications.
Results and discussions
The detailed synthesis procedures of polymers R-/S-P are outlined in Scheme 1. Two chiral
monomers, (R- or S-)-3,3’-diethynyl-2,2’-bis(octyloxy)-1,1’-binaphthalene (R-M-1 or S-M-1) and
AIE-active monomer, 1,2-bis(4-azidophenyl)-1,2-diphenylethene (M-2), could be synthesized
according to the reported literatures.[20] Chiral polymer R-P could be synthesized by click
polymerization reaction (specifically Azide-Alkyne Huisgen Cycloaddition) of R-M-1 and M-2 in
about 76% yield, and chiral polymer S-P was obtained by click polymerization reaction of S-M-1
and M-2 in about 80% yield. The thermal stability of R-P is evaluated by thermogravimetric
analysis (TGA). It loses 5% of its original weight when it is heated to a temperature of about 330
(Td), which indicates better thermal stability. In addition, the resulting polymers have moderate
yields and molecular weights (R-P: Mn =9240, PDI = 1.43; S-P: Mn =8227, PDI = 1.41). In the 1H
NMR spectrum of R-/S-P, the peaks at 3.31 ppm from the acetylene proton resonance completely
disappear, which can also demonstrate the effective click polymerization reaction between chiral
monomer M-1 and M-2. The target product can also show excellent solubility in common solvents,
such as THF, CH2Cl2, CHCl3, which can be due to the flexible n-octyl group substituents from
binaphthyl moiety.

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Scheme 1. Synthesis procedures of S-M-1, R-M-1, M-2, R-P and S-P.
In this paper, we first investigated their UV-vis absorption and fluorescent emission spectra in
THF and THF-H2O mixed solvents at a fixed concentration (5.0 × 10-5 mol L−1 corresponding to
binaphthyl moiety), respectively. As shown in Figure 1, R-/S-P have two absorption bands at 255
nm and 298 nm, which can be regarded as the π-π* transition of binaphthyl moiety. The maximum
UV-vis absorption λmax wide band centered at around 345 nm can be assigned to the conjugated
polymer backbones. Furthermore, UV-vis absorption spectra were carried out by changing the
different water fraction (fw) in THF-H2O mixtures. As fw increases to 80%, obvious red shift
(about 8 nm) can be observed relative to the absorption band in pure THF solution. The relative
intensity of absorption peaks doesn’t show obvious change until poor solvent water fraction fw
increases up to 90%. But as the further increase of water, the whole UV-vis absorption shows
great decrease at fw = 95% and 99%, which may be attributed to the reason that the polymer
aggregate nanoparicles tend to form the precipatation at high water fraction.

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As is evident from Figure 2, we found that R-/S-P in THF solution show weak fluorescence
emission centered at 435 nm with 1.3% of quantum yield. Upon the addition of water, AIE-active
R-/S-P can emit the gradual enhancement fluorescence signal with 60 nm red-shift to 495 nm and
reach the strongest emission intensity (ΦPL=12.3%) at fw = 80%, which can be assigned to the
effective π-π* congugated effect in the aggregate state. As shown in the insert of Figure 2, bright
blue-green color can be clearly observed under a commercially available UV lamp. But like
UV-vis absorption, the fluorescence signals appear obvious decrease as the further increase of
water at fw = 90%, 95% and 99%.
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
f (vol%)
w
0
20
40
60
80
90
95
99
250
300
350
400
450
500
550
600
Wavelength (nm)
Figure 1. UV-vis absorption spectra of R-/S-P in THF-water mixtures at a fixed concentration
(5.0 × 10-5 mol L−1, scanning rate: 200 nm/min, cell length: 10 mm).

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6
5
4
3
2
3500
3000
2500
2000
1500
1000
500
0% 80%
1
0
20 40 60 80 100
Water Fraction (vol%)
0
20
40
60
80
90
95
99
f (vol%)
w
0
450
500
550
600
650
Wavelength (nm)
Figure 2. Fluorescence emission spectra of R-/S-P in THF-water mixtures at a fixed concentration
(5.0 × 10-5 mol L−1, λex = 350 nm, bandwidth for emission: 5 nm, bandwidth for excitation: 5 nm,
scanning rate: 200 nm/min, cell length: 10 mm). Inset: Plot of (I/I0) values versus the
compositions of the aqueous mixtures.
The CD spectra of R-/S-P were performed in THF solution (5.0 × 10-5 mol L−1) and exhibits clear
mirror image CD bands (Figure 3). According to the reported literature, the chiral BINOL can
exhibit three characteristic CD signals, one weaker band at around 300 nm and two stronger bands
at about 225 nm and 240 nm.[21] Taken S-P as an example, the CD spectra display three obvious
peaks at 250 nm, 267 nm and 342 nm. Among them, strong negative Cotton effects at 250 nm and
positive Cotton effects at 267nm can be assigned to the feature skeleton absorption of
(S)-binaphthyl moiety in the main chain of the polymer, while the long wavelength CD effect
appears at 342 nm, which can be regarded as the extended conjugated structure in the repeating
unit and a high rigidity of polymer backbone. The absorption dissymmetry factor (gabs), which
defined as gabs = 2(εL-εR) /(εL+εR) =∆ε/ε, can reach as high as 5.78 × 10-4 for S-P and -6.25 × 10-4
for R-P, respectively. To further investigate the CD spectrum change feature of R-/S-P in the
aggregate state, we found that the intensity of CD signal gradually declines as the increase of
water fraction over 40%, which may be due to the concentration decrease of the dispersed polymer

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chains in THF-H2O mixed system.
f (vol%)
w
S-0
(a)
S-20
S-40
S-60
S-80
S-90
S-95
S-99
8
4
0
-4
-8
-12
250
300
350
400
450
500
550
600
Wavelength (nm)
f (vol%)
w
(b)
R-0
12
R-20
R-40
R-60
R-80
R-90
R-95
R-99
8
4
0
-4
-8
250
300
350
400
450
500
550
600
Wavelength (nm)
Figure 3. CD spectra of (a) R-P and (b) S-P in THF and THF-water mixtures at a fixed
concentration (5.0 × 10-5 mol L−1, scanning rate: 200 nm/min, cell length: 1 mm)
The AIE-active conjugated polymers R-/S-P can display strong aggregation-induced fluorescence
enhancement responses in the aggregate state, which inspires us to further investigate their
aggregation-induced CPL behaviour. Seen as a fundamental parameter of CPL, the luminescence
dissymmetry factor (glum) value can be evaluated by using the equation glum = 2(IL-IR)/(IL+IR),
where IL and IR are the emission intensities of left and right circularly polarized luminescence,
respectively. As is evident from Figure 4, almost no CPL emission signal can be detected in THF

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solution because R-/S-P are nearly non-luminescent. However, R-/S-P appear obvious CPL
response signal (glum = -1.87 × 10-3 for R-P, +4.12 × 10-3 for S-P) at fw = 40%, indicating the
gradual intramolecular chirality transfer via the conjugated polymer chain backbone structure.
Meanwhile, it can be found that the aggregation-induced CPL of polymers R-/S-P can exhibit
good mirror–image, and the emission peak situated at 490 nm-500 nm can also coincide well with
their fluorescence spectra in the aggregate state. The AICPL signals can reach the strongest
emission (glum = -5.64 × 10-3 for R-P, +6.97 × 10-3 for S-P) at fw = 90%, but tend to decrease
(Figure S10) while the further addition of water to 99% (glum = -4.12 × 10-3 for R-P, +4.26 × 10-3
for S-P) due to the precipitate formation at high H2O fraction. We infer that the AIE-active R-/S-P
can form the regular and orderly self-assembly nanoparticles in the aggregate state leading to
AICPL emission enlargement effect. [11]
f (vol%)
w
0
30
20
40
80
90
95
20
99
10
0
-10
-20
450
500
550
600
650
Wavelength (nm)
Figure 4. CPL spectra of R-/S-P in THF and THF-water mixtures at a fixed concentration (5.0 ×
10-5 mol L−1, λex = 350 nm, bandwidth for emission: 3000 µm, bandwidth for excitation: 3000 µm,
scanning rate: 200 nm/min, cell length: 10 mm).
To well understand the AICPL response enhancement mechanism of the polymers R-/S-P in the
aggregation, we further investigated the morphologies of aggregates in different THF-H2O
mixtures by using scanning electron microscopy (SEM) measurements. In the supramolecular

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self-assemble process, we found that the surface profile of free polymer chain forms regularly
sphere nanoparticles at fw = 40% (Figure 5a). As the further increase of water fraction up to fw =
80%, the sphere aggregates of S-P gradually transform as left-handed helical nanowires via
supramolecular self-assembly as shown in Figure 5b. Interestingly, these supramolecular
self-assembled helical nanowires appear more twisted nanowires (Figure 5c) at fw = 90% and even
intertwine with each other (Figure 5d) at fw = 95%. As is evident from Figure S15, the helical
nanofibers further coiled in the end to form several irregular rings as the increase of water fraction
up to 99%. We can draw the conclusion that obvious decrease of UV-vis absorption, CD,
fluorescence and AICPL emission signals can be attributed to the precipitate formation at high
poor solvent fraction. As shown in Figure S12, we also observed that R-P self-assembled the same
left-handed helical nanowires as S-P in the THF-H2O mixtures. No expected handedness inversion
indicates that the driving force for the formation of helical nanowires are not only from the π-π
interactions influenced by binaphthyl chirality, but also from the cooperate effects of multiple
intermolecular hydrogen bonding (N-H…O, C-H…O, C-H…N) and steric effects. [22]
Figure 5. SEM images of S-P at (a) 40, (b) 80, (c) 90, (d) 95 vol% (fw)
Considering that practical applications in emitting devices usually demand a solid state active

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layer, we explored CPL emission of polymers R-/S-P in the cast-spin film. As shown in Figure 6,
R-/S-P in the cast-film can exhibit stronger CPL response than in the solution at around 490 nm.
Compared with the maximum response in solution, the glum values of S-P and R-P in the cast-spin
film are 1.45 × 10-2 and 0.82 × 10-2, amplified up to 2.08 times and 1.45 times respectively.
Taking note of the fact that stronger π-π interactions between polymers will be created in the solid
state in contrast to in the solution system, we suppose that the amplification effect in the cast-spin
film is caused by the more highly ordered aggregated structures.[11,23,24]
60
40
Film from S-P
Film from R-P
20
0
-20
-40
-60
450
500
550
600
650
Wavelength (nm)
Figure 6. CPL spectra of R-/S-P in the cast-spin film (λex = 350 nm, bandwidth for emission:
3000 µm, bandwidth for excitation: 3000 µm, scanning rate: 200 nm/min).
Conclusions
In summary, we have designed and synthesized a pair of AIE-active chiral conjugated polymers
enantiomers via click reaction. The CD and CPL spectra reveal the effective chiral transfer from
chiral binaphthal moieties to AIE-active TPE chromophore via conjugated chain backbone
structure. The dissymmetry factor glum can reach as high as 6.97 × 10-3 and 1.45 × 10-2 in the
aggregate and cast-spin film, respectively. The SEM images show that chiral conjugated polymers

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R-/S-P can self-assemble as helical nanowires leading to the AICPL response behavior at
particular THF-H2O mixtures.
Experimental Section
Measurements and materials.
All the solvents and reagents were commercially available and analytical grade. THF and Et3N
were distilled from sodium in the presence of benzophenone. NMR spectra were obtained by
1
using Bruker AVANCE III-400 spectrometer with 400 MHz for H NMR and 100 MHz for 13C
NMR, and the chemical shifts are reported as parts per million (ppm) relative to tetramethylsilane
(TMS) as internal standard. Circular dichroism (CD) spectra were recorded on a JASCO J-810
spectropolarimeter, and the length of the sample cell was 0.1 cm. Circularly polarized
luminescence (CPL) spectra were recorded with a JASCO CPL-300 spectrofluoropolarimeter. In
the CPL measurements, the excitation wavelength was 350 nm, scan speed was 200 nm/min,
number of scans was 1, and slit width was 3000 µm. The magnitude of circular polarization in the
excited state is defined as glum = 2(IL-IR)/(IL+IR), where IL and IR indicate the output signals for left
and right circularly polarized light, respectively. Experimentally, the value of glum is defined as
glum = Δ I/I = [ellipticity/(32980/ln10)]/(unpolarized PL intensity) at the CPL extremum.
Molecular weight was determined by gel permeation chromatography (GPC) with a Waters 244
HPLC pump, and THF was used as solvent relative to polystyrene standards. Dynamic light
scattering (DLS) measurement was performed on a 90Plus particle size analyzer (Brookhaven
Instruments Co.). Thermogravimetric analyses (TGA) were obtained from a Perkin-Elmer Pyris-1
instrument under N2 atmosphere.
Synthesis of 3,3’-diethynyl-2,2’-bis(octyloxy)-1,1’-binaphthalene (M-1):

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Monomer M-1 was synthesized according to the reported literature. A mixture of compound 2
(2.00 g, 2.62 mmol), ethynyltrimethylsilane (1.28 g, 13.08 mmol), Pd(PPh3)2Cl2 (183.61 mg, 10%
mmol), CuI (49.82 mg, 10% mmol) were added to 10 mL Et3N under N2 atmosphere. The reaction
was stirred at 80 °C for 24 h. After cooling to room temperature, the reaction mixture was filtrated
through a short silica gel column. The solvent was removed to afford crude intermediate product.
K2CO3 (3.91 g, 28.29 mmol) were added into the mixed solvents of 10 ml CH2Cl2 and 10 ml
CH3OH and the previous intermediate product was added. The reaction was stirred overnight and
extracted with CH2Cl2, washed with brine and dried over anhydrous Na2SO4. Then the solvent was
removed, the crude product was purified by column chromatography (petroleum ether) to afford
0.85 g as a white solid in 58% yield. 1H NMR (400 MHz, CDCl3): δ 8.16 (s, 2H), 7.83 (d, J = 8.2
Hz, 2H), 7.39 (m, J = 8.2, 7.1, 1.2 Hz, 2H), 7.26 (m, J=7.1, 1.2 Hz, 2H), 7.14 (d, J = 8.2 Hz, 2H),
4.00 (m, J = 8.7, 6.3 Hz, 2H), 3.70 (m, J = 8.7, 6.3 Hz, 2H), 3.31 (s, 2H), 1.36 – 1.15 (m, 8H),
1.15 – 1.04 (m, 4H), 1.04 – 0.95 (m, 4H), 0.95 – 0.74 (m, 12H), 0.71 – 0.56 (m, 2H). 13C NMR
(100 MHz, CDCl3): δ 155.61, 135.11, 134.31, 130.06, 127.84, 127.41, 126.02, 125.43, 125.30,
116.73, 81.27, 80.98, 77.48, 77.16, 76.84, 73.84, 31.85, 30.08, 29.27, 29.18, 25.55, 22.83, 14.29.
Synthesis of 1,2-bis(4-azidophenyl)-1,2-diphenylethene (M-2):
In a 100 mL three necked round bottom flask were placed 5.7 mL of distilled water and sodium
tetrafluoroborate (1.35 g, 12.5 mmol). The mixture was stirred until all solid was dissolved, and
then 5.7 mL of conc hydrochloric acid was added. The flask was placed in a -20 °C cold bath and
the solution was kept stirring. In a separate flask containing 9.4 mL of distilled water were placed
compound 3 (1.67 g, 4.61 mmol) and sodium nitrite (0.69 g, 10.02 mmol) (minimal heating was
used to dissolve solids). The solution of compound 3 was added dropwise to the reaction flask

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with stirring. The temperature was kept at -20 °C to -15 °C during the addition. The mixture was
stirred for an additional 30 min. The precipitate was collected by filtration, washed with water
followed by ethyl ether, and air dried to give brown solid which was used in next step. In a 200 ml
round bottom flask were placed 38.5 ml of distilled water and sodium azide (0.47 g, 7.23 mmol).
The flask was kept in an ice bath and the previous brown solid was added. The solution was kept
stirring for 30 min and precipitations appeared on the bottom of the flask, which were collected
through filtering to afford crude product (M-2) for further purification. The crude product can be
dissolved in ether and filtered. After the filtrate was evaporated, the residue was purified by
1
column chromatography to give 1.03 g as a yellow solid in 54% yield. H NMR (400 MHz,
CDCl3): δ 7.18-7.11 (m, 6H), 7.05-6.94 (m, 8H), 6.81-6.70 (m, 4H). 13C NMR (100 MHz, CDCl3):
δ 143.44, 140.55, 140.33, 138.19, 132.86, 131.42, 128.09, 126.93, 118.50.
Synthesis of polymer R-/S-P:
M-1 (114.82 mg, 0.21 mmol), M-2 (85.17 mg, 0.21 mmol), Na Ascorbate (16.28 mg, 40 mol%),
.
CuSO4 5H2O (10.26 mg, 20 mol%) were added into the mixed solvents of 6 ml THF and 6 ml H2O.
The solution was stirred at 45 °C for 4 days under N2. The solvents were removed under reduced
pressure and the residue was extracted with CHCl3 (2 × 50 mL). The organic layer was washed
with an aqueous NH4OH solution, water and then dried over anhydrous Na2SO4. After the solution
was removed, the resulting polymer was precipitated into methanol, and then filtered and washed
with methanol several times. The dark yellow polymers were collected and dried in vacuum to
give R-P of 152.0 mg in 76% yield and S-P of 160.3 mg in 80% yield. [α]ꢁꢀꢂ of R-P and S-P
(THF, 1.0 g/1000 ml) are -282.0 and +328.0, respectively; GPC of R-P: Mw = 13200, Mn =9240,
PDI = 1.43, GPC of S-P: Mw = 11600, Mn =8227, PDI = 1.41; Degradation temperature of R-/S-P:

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Td = 330 °C; 1H NMR (400 MHz, CDCl3): δ 8.87 (d, J = 19.2 Hz, 2H), 8.51 (d, J = 15.2 Hz, 2H),
7.95 (d, J = 7.8 Hz, 2H), 7.51 (t, J = 13.7 Hz, 2H), 7.35 (d, J = 6.9 Hz, 2H), 7.25 – 6.90 (m, 18H),
3.52 (s, 2H), 3.15 (s, 2H), 1.24 – 0.91 (m, 10H), 0.82 (m, J = 18.8, 6.9 Hz, 4H), 0.77 – 0.50 (m,
16H), 0.38 (s, 2H).
Spin coating of thin polymer films:
Two films of S-P and R-P samples on ITO-coated glass substrate could be prepared by using
spin-coating method. The corresponding chiral polymer layer is spin-coated from a 10 mg/ml
solution in DMF on ITO-coated glass substrate. The spin speed was gradually increased to 1500
r/min and the spin lasted for about one minute.
Acknowledgment.
This work was supported by the National Natural Science Foundation of China (21674046,
21474048 and 51673093).
Supporting Information.; UV-vis absorption, fluorescence, CD and CPL spectra mentioned in
above paragraphs; TGA, GPC and DLS data, SEM images and 1H NMR spectra of new polymers
as well.
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Highlights
ò
Two chiral conjugated polymer enantiomers R-P and S-P were designed and synthesized via
click polymerization.
ò
ò
The resulting polymers exhibit obvious AIE behavior.
These two polymers can exhibit CPL emission signals in the aggregates and cast-spin films,
and the highest glum value can be up to 6.97 × 10-3 and 1.45 × 10-2, respectively.