Article

Cite This: Macromolecules 2019, 52, 3668−3679 pubs.acs.org/Macromolecules

Design and Synthesis of Luminescent Liquid Crystalline Polymers

with “Jacketing” Effect and Luminescent Patterning Applications
Ji-Chun Zhu,†,# Ting Han,‡,§,# Yang Guo,† Ping Wang,† He-Lou Xie,*,† Zhen-Gong Meng,‡
Zhen-Qiang Yu,*,‡ and Ben Zhong Tang*,§
†
Key Lab of Environment-friendly Chemistry and Application in Ministry of Education, College of Chemistry, Xiangtan University,
Xiangtan 411105, Hunan Province, China
‡
School of Chemistry and Environmental Engineering, College of Materials Science and Engineering, Center for AIE Research,
Shenzhen University, Shenzhen 518060, China
§
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China
*
S Supporting Information

ABSTRACT: To fabricate luminescent liquid crystalline polymers (LLCs),

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two monomers 2,5-bis[(4′,4″-dibutyloxy)tetraphenylphthalate]styrene (M1)

and 2,5-bis[(4′,4″-dibutyloxy)tetraphenylethylene]styrene (M2) have been
successfully designed and synthesized. Although M1 and M2 show no LC
property and M1 is nonemissive in the solid state, M2 shows very strong solid-
state emission with a fluorescence quantum yield (ΦF) of 27.7%. The better
solid-state luminescence behavior of M2 than M1 can be attributed to the
elimination of the photoinduced electron transfer effect as suggested by the
theoretical calculation results. The structural difference between M1 and M2
also results in a dramatical difference of polymerizability. While M1 can be
readily homopolymerized using the radical polymerization method, M2 can
only be copolymerized under harsh conditions. The resulting homopolymer
poly{2,5-bis[2-(4,4′-dibutyloxy)tetraphenylphthalate]styrene} (P0) and co-
polymers poly{2,5-bis[(4′,4″-dibutyloxy)tetraphenylethylene] styrene}x−{[2,5-di(hexylformate)]styrene}y (Pns, n = 1, 2, 3) all
show typical columnar liquid crystal phase (ColH) as demonstrated by the variable-temperature 1D wide-angle X-ray diffraction
results. Similar to their corresponding monomers, P0 is weakly emissive with a low ΦF of 2.0% in the solid state whereas Pns
exhibit strong solid-state fluorescence with ΦF in the range 18.0−45.1%. The ΦF value of the copolymers increases with the
increasing contents of composition M2. The obtained Pns with good solution processability can be used to prepare highly
luminescent two-dimensional patterns with high resolution through nanoimprint lithography, which reveals that Pns find
potential applications in advanced optoelectronic and biophotonic devices.

■ INTRODUCTION
Luminescent liquid crystals (LLCs) combining luminescent
properties and ordered structures of liquid crystals (LC) have
attracted great attention due to their significant applications in
organic light-emitting diodes, luminescent liquid crystal
displays, sensors, and optical storage information.1−7 The
formation of ordered LC structure for LLCs generally requires
the regular packing in solid state. Unfortunately, conventional
luminophores in LLCs with rod- or disc-like shapes tend to
form excimeric species due to the presence of strong π−π
stacking interactions in solid states. The excited states of the
luminophore aggregates usually descent to the ground state
through nonradiative relaxation pathways to lead to the
emissive quenching of the luminophores, and thus conven-
tional LLCs often show an aggregation-caused quenching
(ACQ) phenomenon.8−13 This phenomenon seriously limits
the practical applications of LLCs. Therefore, how to
reasonably design and fabricate LLCs with high emission
efficiency has become a very interesting and significant
research field.14−20
Aggregation-induced emission (AIE) proposed by Tang and
co-workers in 2001 is a photophysical phenomenon that is
completely opposite to ACQ.21 Generally, luminogens with
AIE effect (AIEgens) are weakly or even nonemissive in dilute
solutions due to the intramolecular motions which results in
the dissipation of excited-state energy via nonradiative
relaxation channel approach.22−24 However, the intramolecular
motions can be restricted due to physical constraints in the
aggregate or solid states, and thus the excited state of the
luminogen can decay radiatively to the ground state to induce
or enhance the fluorescence of the luminogens.25−30 Thus, it
becomes a good strategy to solve the emission quenching issue
of conventional LLCs and fabricate highly luminescent LLCs
Received: January 31, 2019
Revised: April 8, 2019
Published: May 7, 2019

© 2019 American Chemical Society 3668 DOI: 10.1021/acs.macromol.9b00221

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by introducing AIEgen as the substituent groups into the LC
mesogens.31−37
As a typical AIEgen, tetraphenylethylene (TPE) shows
highly efficient solid-state luminescence because of its twisted
“propeller-like” structure.38−42 By modifying the periphery of
TPE molecule with suitable substituent groups, such as alkane
and LC mesogens, different LLCs have been fabricated.43,44
These LLCs can show high luminescence efficiency and
various LC phase structures.45−49 For example, LLCs with
TPE as the luminescent core have been reported to show
rectangular columnar and hexagonal columnar phase depend-
ent on the tail chains. The emission color can be rapidly and
reversibly tuned from sky blue to green.50 The LLC with rod-
shaped LC moieties as the periphery and TPE as core not only
shows high solid-state luminescence efficiency but also exhibits
a unique biaxial oriented structure.51 In addition to small
molecules, luminescent liquid crystalline polymers (LLCPs)
have also been successfully prepared by copolymerizing the
mesogens and TPE luminogens.52
On the basis of the AIE and “jacket” effect, we have
successfully fabricated a series of TPE-containing LLCPs in
our previous work.53 The “jacket” effect comes from the special
mesogen-jacketed liquid crystalline polymers (MJLCPs),54
which is a kind of LCPs with bulky side groups attached to
the polymer main chain through a very short spacer or without
spacer. The bulky side groups of MJLCPs do not have to be
mesogenic and can serve as a “jacket” around each chain
backbone. Because of the steric requirements of the “jacket”,
the main chain of the resultant LCPs can be forced to show an
extended conformation.55,56 The obtained LLCPs with differ-
ent spacer length can show smectic A phase and the columnar
phase. Meanwhile, with the decrease of the spacer length, the
fluorescence quantum yield (ΦF) of the LLCPs dramatically
increases. On the basis of this idea, herein we intend to further
design and synthesize new highly luminescent LLCPs without
spacers by directly connecting the TPE moiety on the 2- and 5-
position of a styrene through the ester bonds or carbon−
carbon bonds. The resulting monomer without ester groups
(M2) shows a much higher solid-state ΦF value of 27.7% than
that of the monomer with ester groups (M1). Although both
monomers possess vinyl groups, M1 can be easily polymerized
by radical homopolymerizations while M2 is hard to be
homopolymerized possibly due to the poorer solubility and
larger structural steric hindrance of M2. Therefore, further
copolymerization was implemented for monomer M2. The
chemical structures of the resultant polymers are shown in
Scheme 1. All the obtained polymers show typical LC
behavior, and all copolymers (Pns) show obvious AIE
properties. By utilizing the good solution processability and
high solid-state fluorescence of Pns, well-resolved fluorescent
two-dimensional patterns were readily fabricated through the
nanoimprint lithography.
■
EXPERIMENTAL SECTION
Synthesis of M1 and P0. The synthetic route of M1 and P0 is
shown in Scheme 2. The detailed synthesis information about the
intermediates is shown in the Supporting Information, and the
information about monomer and polymer is described as follows.
Synthesis of 2,5-Bis[2-(4,4′-Dibutyloxytetraphenyl-
phthalate)]styrene (M1). In a 250 mL round-bottom flask
equipped with a magnetic stirrer was added vinyl terephthalic acid
(0.63 g, 3.30 mmol), 120 mL of dichloromethane, 1.3 mL of oxalyl
chloride, and 2 drops of DMF. The acid chloride reaction was
complete until the solution becomes clear. The remaining oxalyl
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Scheme 1. Molecular Structures of P0 and Pns
chloride was carried away with dichloromethane through the rotary
evaporator, and this procedure was repeated three times until the
oxalyl chloride was completely removed. Then 4,4′-dibutyloxyte-
trastyrene (4.20 g, 7.58 mmol) was dissolved in 150 mL of distilled
THF in a 250 mL magnet-containing round-bottom flask followed by
the addition of triethylamine (5.2 mL, 37.90 mmol). Then the
prepared vinyl terephthalate chloride was dissolved in THF and added
dropwise into the reaction an ice bath. After the dropwise addition,
the reaction was performed at room temperature for 12 h. After
completion of the reaction, 1 mL of water was added dropwise to
quench the reaction, and the resulting white precipitate was removed
by suction filtration. Then THF solvent was removed by rotary
evaporation. The product was purified by column chromatography on
silica gel with dichloromethane:petroleum ether = 2:1 (v/v) as eluent.
Yield: 85%. 1H NMR (CDCl3) δ (ppm): 8.42 (d, 1H, Ar−H), 8.13
(d, 2 H, Ar−H), 7.21−6.61 (m,34 H, Ar−H), 7.41 (t, 1 H, −CH
CH2−), 5.83 (t, 1 H, −CHCH2−), 5.54 (m, 1 H, −CHCH2−),
3.95 (m, 8 H, −OCH2−), 1.77 (t, 8 H, −CH2−). 1.32−1.51 (t, 8 H,
−CH2−), 0.95 (t, 12 H, −CH3). 13C NMR δ (ppm): 164.8 (CO),
164.1 (CO), 157.77−157.85 (phenyl C−O), 148.71−148.81
(phenyl C−O−CO), 142.35−142.39 (CC), 140.60−140.84
(phenyl C−CC), 137.92 (aromatic C−CHCH2), 137.92
(phenyl C−CC), 135.94 (aromatic C−CO), 134 (aromatic
−C−CCH−), 133.23 (aromatic meta C−CHCH2), 118.41−
132.61 (phenyl C), 114 (CH2), 67.52−67.54 (−OCH2−), 29.71−
31.39 (−CH2−), 19.27 (−CH2−), 13.89 (−CH3). IR (ATR, cm−1):
3051, 985.57 (HCCH2) 2930.51, 2857.41 (−CH2−), 3051.32,
1603.64, 1491.57, 759.93, 746.77, 696.18 (−Ar), 1716.25 (CO),
1380.06 (−CH3), 1387.71, 842.45 (−CC−). Melting point (mp):
200 °C.
Synthesis of Poly(2,5-bis[2-(4,4′-dibutyloxy)tetra-
phenylphthalate]styrene) (P0). The monomer 2,5-bis[2-(4,4′-
dibutyloxytetrastyrene)]vinyl terephthalate (1.052 g, 0.92 mmol) and
initiator AIBN (1 mg/mL, 0.1 mL) were sequentially added to the
polymerization tube, and distilled THF was added as the solvent to
make the mass fraction of the monomer be 30%. After three times of
freezing and three times of melting, the tube was sealed under
vacuum. The polymerization tube was stirred in an oil bath at 60 °C
for 12 h. Afterward, the polymerization tube was opened, and the
polymerization solution was diluted with three times of THF solvent.
The diluted polymerization solution was added dropwise into
methanol to precipitate the polymeric products, and the sedimenta-
tion process was repeated twice to remove the monomer. The
obtained precipitate was collected and dried in a vacuum oven at 30
°C overnight. Yield: 75%.
Synthesis of M2 and Pns. The synthetic routes of M2 and Pns
are shown in Scheme 3. The detailed synthesis information about the
intermediates is shown in the Supporting Information, and the
information about monomer and polymer is described as follows.
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Scheme 2. Synthetic Routes of M1 and P0
Scheme 3. Synthetic Routes of M2 and Pns
Synthesis of 2,5-Bis[(4′,4″-dibutyloxy)-
tetraphenylethylene]styrene (M2). 4′,4″-Dibutyloxy-
tetraphenylethylene-4-borate (1.5 g, 2.50 mmol), potassium carbonate
(0.7 g, 5.10 mmol), phase transfer catalyst (methyltrioctylammonium
chloride), 2,5-dibromostyrene (0.325 g, 1.25 mmol), and tetrakis-
(triphenylphosphine)palladium (0.1 g, 0.087 mmol) were added into
a 250 mL three-necked flask. The mixture was evacuated first and
then bubbled through N2 for three consecutive times. Finally, 90 mL
of toluene/H2O (2:1) was injected into the mixture as solvent, and
the mixture was stirred in an oil bath at 90 °C for 24 h. The obtained
crude product was extracted with H2O/DCM (3:1) and then purified
by column chromatography on silica gel (petroleum ether:DCM =
4:1). Yield: 50%. 1H NMR (CDCl3) δ (ppm): 7.79 (s, 1 H, Ar−H),
7.48 (m, 2 H, Ar−H), 7.4 (m, 1 H, Ar−H), 7.32 (m, 1 H, Ar−H),
7.12 (m, 16 H, Ar−H), 6.95 (m, 8 H, Ar−H), 6.64 (m, 8 H, Ar−H),
6.7 (m, 1 H, −CHCH2), 5.69 (d, 1 H, −CHCH2), 5.2 (d, 1 H,
−CHCH2), 3.89 (m, 8 H, −OCH2−), 1.73 (s, 8 H, −CH2−), 1.46
(s, 8 H, −CH2−), 0.98 (s, 12 H, −CH3). 13CNMR: 158 (TPE C−O),
148.71−148.81 (TPE CHCH−C), 142.35−142.39 (TPE −C
C−), 138.69−139.67 (phenyl C−CC), 138.53 (aromatic C−CH
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CH2), 137.95 (phenyl C−CC), 136.20 (aromatic −C−CCH−),
133.95 (aromatic meta C−CHCH2), 113.48−132.68 (phenyl C),
114.68 (CH 2), 67.48 (−OCH 2−), 31.4 (−CH 2−), 19.30
(−CH2−), 13.94 (−CH3). IR (ATR, cm−1): 3023.12, 1287.24
(HCCH2), 2920.16, 2864.14 (−CH2−), 3023.95, 1600.31,
1569.78, 1501.66, 1244.23, 1170.63, 1011.19, 912.32, 814.97 (−Ar),
2957.36, 1385.51 (−CH3), 1385.51, 864.22 (−CC−). MS
(MALDI-TOF MS): m/z [M]+ calcd for C76H76O4, 1052.6; found,
1052.6. Melting point (mp): 150 °C.
Synthesis of Copolymer Poly(2,5-bis[(4′,4″-dibutyloxy)-
tetraphenylethylene]styrene) x −(2,5-Di(hexylformate)]-
styrene)y (Pns). Into a polymerization tube was added 0.5 g (0.475
mmol) of 2,5-bis[(4′,4″-dibutyloxy)tetraphenylethylene]styrene
(M2), 5 μL of tert-butyl hydroperoxide, and 0.7 g (1.9 mmol) of
[2,5-di(hexylformate)]styrene (HCS). Subsequently, the reaction was
purged with argon, and the reaction was polymerized at 170 °C for 10
h. Yield for P1: 60%. The quantities of M2 and HCS used for the
synthesis of copolymer P2 are 0.5 g (0.475 mmol) and 0.264 g (0.712
mmol), respectively. Yield for P2: 56%. The quantities of M2 and
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HCS used for the synthesis of copolymer P3 are 0.5 g (0.475 mmol)
and 0.117 g (0.317 mmol), respectively. Yield for P3: 54%.
■
RESULTS AND DISCUSSION
Synthesis and Characterization of Polymers. Mono-
mers M1 and M2 were successfully prepared according to the
synthetic route shown in Schemes 2 and 3, whose chemical
structures were verified by combined characterization methods.
Although both monomers were styrene derivatives, only M1
was able to be readily polymerized using the radical
polymerization method. After polymerization, all characteristic
peaks associated with the resonances of the vinyl substituent in
M1 at 5.50 ppm (peak a), 5.80 ppm (peak b), and 7.52 ppm
(peak c) disappeared (see Figure S1 and Figure 1a). In the
Figure 1. 1H NMR spectra of (a) P0 and (b) Pns (P1, P2, and P3) in
CDCl3.
meantime, the resonance peaks of the polymer P0 were much
broader than those of the corresponding monomer (M1),
suggesting its polymeric nature. GPC results showed that the
number-average molecular weight (Mn) and polydispersity
index (PDI) of P0 were 9.10 × 105 and 1.98, respectively.
However, the same polymerization process did not work for
M2 whose structure was similar to M1 but without ester
groups. We also tried to conduct the polymerizations of M2 in
different solvents and different polymerization temperatures,
but all experiments failed.
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Compared to its analogue M1, M2 showed much poorer
solubility in most organic solvents due to its more rigid
structure with larger steric hindrance, which could be the
crucial reason for the poor homopolymerizability of M2. To
solve this problem, a bulk polymerization was employed and
the polymerization was conducted at ∼170 °C, which slightly
exceeded the melting point of M2 (150 °C). tert-Butyl
hydroperoxide with a half-life period of 10 h at 170 °C was
used as the initiator. To facilitate the polymerization,
comonomers with smaller steric hindrance were used to
copolymerize with M2. Because of the low boiling point of the
commonly used commercial monomers such as styrene and
methyl methacrylate, the lab-made [2,5-di(hexylformate)]-
styrene (HCS)57 with high boiling point was employed in this
system. By controlling the feed ratios, three copolymers (Pns, n
= 1, 2, 3) with different contents of M2 and HCS were
successfully achieved. The resulting copolymers showed very
good solubility in common solvents, such as acetone, THF,
toluene, chlorobenzene, and dichloromethane. As shown in
Figure S2, the resonance signals of monomer M2 at 7.79 ppm
(peak a) and 7.48 ppm (peak b) are assigned as the
characteristic peaks of the phenyl protons adjacent to the
vinyl group while those at 5.20 ppm (peak i), 5.72 ppm (peak
j), and 6.70 ppm (peak k) are characteristic peaks of the vinyl
substituent. The resonance peaks in the region of 6.64−7.40
ppm (peaks c, d, e, f, g, and h) were ascribed to the
characteristic peaks of the TPE substituents, and the rest of
peaks at 3.92 ppm (peak l), 1.76 ppm (peak m), 1.45 ppm
(peak n), and 0.98 ppm (peak o) were related to the
resonances of alkoxy protons. After the copolymerizations,
peaks i, j, and k associated with the vinyl substituent clearly
disappeared in the 1H NMR spectra of Pns (Figure 1b).
Meanwhile, the peaks of the polymers became broader
compared to the peaks of corresponding monomer, which
was in good consistence with the formation of expected
polymeric structures. The peaks at “s” and “t” positions were
assigned to the characteristic resonances of HCS, and the
broad peak at 3.75 ppm was related to the characteristic
resonance of the “l” and “p” protons in HCS and M2. On the
basis of the integrals of the circled area, we further calculated
the content of each composition in the copolymers according
to the equations
8y = 1
8x + 4y = a
where a represents the integral area of the “l” and “p” peaks as
labeled in Figure 1. As summarized in Table 1, the final
content of M2 in copolymers P1, P2, and P3 is calculated to
be 18.0, 32.4, and 45.1%, respectively. It was worth noting that
Table 1. Composition and GPC Results of P0, P1, P2, and
P3
monomer feed molar the content of the content of Mnb
ratio [HCS]:[M2] HCSa (%) M2a (%) (×104)
P0 91
P1 4:1 82.0 18.0 1.25
P2 3:2 67.6 32.4 1.04
P3 2:3 54.9 45.1 0.67
a
Determined by the calculation results according to the 1H NMR
spectra. bDetermined by GPC measurements in THF on the basis of a
linear polystyrene calibration.
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Figure 2. DSC thermograms of P0, P1, P2, and P3 recorded under nitrogen at a rate 10 °C/min during the first cooling cycle (a) and the second
heating cycle (b).

the content of each composition in the polymer structures did

not match the corresponding feed ratio because of the different
activity of these two monomers. The GPC results of the
obtained polymers are also depicted in Table 1.
Phase Transitions and LC Property. TGA results
suggested that the obtained LLCPs possessed very good
thermal stabilities. The decomposition temperature of P0 and
Pns at 5% weight loss was higher than 300 °C in an air
atmosphere and was ∼350 °C in a nitrogen atmosphere.
Subsequently, the DSC experiments were performed to
investigate the phase transitions. First heating to 230 °C was
performed at a rate of 20 °C/min and then followed by an
isothermal annealing process for 5 min to eliminate the
thermal history. The DSC trace were further recorded at 10
°C/min. As shown in Figure 2, the DSC thermograms of the
polymers only show a glass transition temperature (Tg), which
is the typical characteristic of MJLCPs. Moreover, the Tg value
increased with the increase of the content of M2, which could
be attributed to the larger side group of M2 than that of HCS.
PLM results indicated that the obtained two monomers Figure 3. Representative textures of P0 (a), P1 (b), P2 (c), and P3
could show typical crystalline birefringence phenomenon (d) at 140 °C (50× magnification).
below the melting point. The birefringence of the crystal
disappears once the temperature exceeded the melting point.
However, obvious birefringence phenomenon can be observed that M1 and M2 formed a crystalline state (Figure S3). For P0,
for P0 as the temperature was beyond Tg. The clearing point during the variable temperature process, a strong diffraction
did not appear before the decomposition, and meanwhile the peak at around 2θ = 3.00° and a very weak diffraction peak at
birefringence phenomenon remained in the cooling process. around 2θ = 5.11° in the low angle region together with a
These results indicated that its liquid crystal phase was diffuse diffraction halo at 2θ = 19.0° in the high angle region
relatively stable. For P1−P3, all copolymers did not exhibit were observed (see Figure 4a,b). Although the two diffraction
birefringence during the heating process. However, when shear peaks were slightly shifted due to the cold shrinkage and
force was implemented, the birefringence phenomenon quickly thermal expansion, the ratio of the two peaks always remained
appeared (see Figure 3). This observation could be explained at 1:31/2, indicating that a stable hexagonal columnar phase was
by the change of the size of the LC domains. The LC domains formed during the whole variable temperature process. Further
were too small to be observed in the initial state. The calculating results showed the columnar diameter was ∼3.43
application of external inducing could prompt the small LC nm. As the temperature increased, the intensity of the
domains to agglomerate into big domains with sizes that are diffraction peak in the low-angle region became stronger and
enough to be observed. the half-peak width became narrower, suggesting that the
To gain further insight into phase structures, one-dimen- domain region of the supramolecular structure was improved.
sional temperature-variable X-ray diffraction (1D-WAXD) A similar phenomenon was observed for the copolymers. As
experiments were carried out. The 1D-WAXD results revealed shown in Figure 4c,d, two peaks at around 2θ = 4.01° and 2θ =
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Figure 4. 1D WAXD profiles of P0 (a, b) and P3 (c, d) recorded at various temperatures upon heating (a, c) and cooling (b, d).
7.11° in low angle region and one diffused halo at
approximately 2θ = 20.0° were observed for P3 during the
whole variable temperature process, which also proves the
formation of typical hexagonal columnar phase with the
diameter of 2.55 nm. The 1D-WAXD results of P1 and P2 (see
Figure S4) showed peaks at similar positions to those of P3 in
the small- and wide-angle regions, indicating that the change in
the content of M2 had little effect on the stacked way of the
molecules.
Photophysical Properties of the Monomers. The
photophysical properties of the monomers were investigated
in THF solution and in THF/water mixtures with different
water fractions (f w). As shown in Figure S5, the absorption
spectra of the THF solutions of M1 and M2 are peaked at 316
and 350 nm, respectively. The red-shifted absorption wave-
length of M2 in comparison to M1 can be attributed to the
larger conjugated structure of M2 arising from the elimination
of ester bonds.
With the well-known AIEgen TPE in the structures, both
monomers were expected to be AIE-active. To verify this
conjecture, the photoluminescence (PL) spectra of M1 and
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M2 in THF and THF/water mixtures with different f w were
investigated. As depicted in Figure 5a,b, with the gradual
addition of water, a nonsolvent of M1 into the THF solution,
the PL spectra first remained almost unchanged when f w was
lower than 60%, and then an obvious emission band peaked at
∼520 nm was observed at higher f w. Although the PL intensity
of M1 aggregates in THF/water mixture with 90% water
fraction at 520 nm was detected to be over 10-fold higher than
that in THF solution, no obvious luminescence can be
observed by naked eyes (see the inset in Figure 5b). The ΦF
value of M1 was measured to be almost zero in both the
solution and solid state. Therefore, both the THF solution and
the aggregated states of M1 were nonemissive despite the
presence of the typical AIE-active moiety in its structure. By
contrast, M2 showed an obvious AIE phenomenon. As shown
in Figure 5c,d, the THF solution of M2 is almost nonemissive,
and the corresponding PL spectrum is basically a flat line
parallel to the abscissa. When the f w of the THF/water mixture
reached 60%, M2 became emissive. Further increase of the
water content greatly enhances the PL intensity. Bright
luminescence could be observed at f w of 80% and 90% with
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Figure 5. (a, c) Emission spectra of M1 (a) and M2 (c) in THF and THF/water mixtures with varied volume fraction of water ( f w). (b, d) Plots of
relative PL intensity (I/I0) at 520 nm (for M1) and at 502 nm (for M2) versus the composition of the aqueous mixtures of M1 (b) and M2 (d).
Inset: fluorescence photos of M1 and M2 in THF with a f w of 0 and 90% taken under 365 nm UV light irradiation. Solution concentration: 10−5 M;
excitation wavelength: 365 nm.

the wavelength of the emission maximum (λem) at 502 nm.
The maximum PL enhancement of M2 was attained at a f w of
90%, whose PL intensity was almost 130-fold that in the THF
solution. The ΦF value of M2 in THF solution and solid state
was measured to be 0.1% and 27.7%, respectively. These
results clearly indicated that M2 was AIE-active. Compared to
our previous work, the luminous efficiency was almost 5.6-fold
higher than that of the previously reported best monomers.53
From the structural point of view, the only difference
between M1 and M2 was the presence of an ester group in M1.
The TPE moiety and the styrene moiety were linked via the
ester group in M1 while the TPE moiety was directly
connected to the styrene moiety in the structure of M2.
However, M1 and M2 showed obviously different luminescent
properties especially in the solid state. To investigate the
electronic structure effect on the luminescence behavior of M1
and M2, the density functional theory (DFT) calculations were
performed using the B3LYP functional with the 6-31G(d,p)
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basis set. The calculated highest occupied molecular orbital
(HOMO) and lowest unoccupied molecular orbital (LUMO)
plots of M1 and M2 are depicted in Figure 6. For M1, the
LUMO was localized over the TPE and styrene moieties while
the HOMO was mainly concentrated on the TPE moiety. The
obvious variation in the electron density distributions of the
HOMO and LUMO of M1 indicated that M1 possesses a
donor−acceptor structure and thus allows it to undergo a
photoinduced electron transfer (PET) process.58−60 Therefore,
the weak luminescence of M1 in both solution and aggregated
states could be possibly attributed to the fluorescence
quenching effect of the PET process. For M2, the removal of
ester groups enabled the electron communication between the
TPE and styrene moieties and thus resulted in the extended
π−π conjugated structure. The DFT result of M2 revealed that
the electron cloud distribution of its HOMO and LUMO was
similar, suggesting that the PET process was blocked by the
small variation of the molecular structure. Therefore, M2 was
DOI: 10.1021/acs.macromol.9b00221
Macromolecules 2019, 52, 3668−3679
Macromolecules
Figure 6. Molecular orbitals of the ground states of M1 and M2 calculated by B3LYP/6-31G(d,p).
able to show strong luminescence in the solid state. In addition
to the electronic structure, the molecular conformations and
motions also have a great influence on the luminescent
properties. In the solution state, M1 and M2 underwent free
and active molecular motions, which would act as a
nonradiative decay pathway for the excitons to result in the
weak luminescence of both M1 and M2 in THF solutions and
aqueous mixtures with a low f w. Upon aggregation formation
or in the solid state, these active motions would be restricted
due to the physical constraint and thus blocked the
nonradiative relaxation pathway, rendering the monomers to
show stronger luminescence. The appearance of the obvious
emission band peaked at ∼520 nm in the PL spectra of M1 at
higher f w and the strong luminescence of M2 in the aggregated
states all supported this mechanism.
Photophysical Properties of the Polymers. The
absorption spectra of P0 and copolymer Pns were measured
and are shown in Figure S5. The absorption maximum of P0
and Pns (P1−P3) was located at 330 and 346 nm,
respectively. The PL behaviors of these polymers were then
investigated. As depicted in Figure 7 and Figure S7, all
polymers showed an aggregation-enhanced emission (AEE)
phenomenon, although the emission enhancement was
obviously different between P0 and Pns due to their structural
difference. In comparison to the monomers, the molecular
motions of the luminogens were partially restricted in nature
due to the polymeric structures. Therefore, these polymers
were emissive in their THF solutions although the intensity
was weak. With the addition of water into the THF solution,
the PL intensity of these polymers gradually increased and
reached the maximum at f w of 90%. Their aggregates showed a
blue-green light emission with at a λem at 502 nm. The ΦF
value of the solid powders of P0, P1, P2, and P3 was measured
to be 2.0, 18.4, 21.0, and 24.3%, respectively, which is much
higher than their ΦF in THF solutions (Table 2). These results
clearly indicated these polymers are AEE-active. In addition, as
summarized in Table 2, the emission enhancement (I90/I0) of
P0, P1, P2, and P3 from the THF solution (I0) to the aqueous
mixture with f w of 90% (I90) was determined to be about 5.0,
18.6, 23.8, and 25.3, respectively. The integral ratio of the
emission area in THF/water mixture with 90% water content
3675
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and in THF solution (A90/A0) was calculated to be 4.5, 17.2,
22.0, and 23.0. These results suggested that the luminescence
performance of P0 was much poorer than that of other
polymers (P1, P2, and P3). The corresponding DFT
calculation results for the simplified P0 structure implied
that the PET effect was not blocked after the polymerization of
M1 (see Figure S8). This explained why the emission of P0
was still weaker than the polymers prepared from M2. An
obvious difference between M1 and P0 was that the
luminescence becomes slightly stronger after polymerization,
and greenish-blue luminescence could be observed in the
aggregate or solid states of P0 by the naked eye, albeit in a
relatively weak intensity. This observation could be rational-
ized by the amplification effect of polymers. The larger steric
hindrance and more rigid conformation of polymer structures
compared to the corresponding monomers could further
restrict the molecular motions in the aggregated states and thus
resulted in the relatively stronger luminescence. On the other
hand, the results in Table 2 also implied that the increase of
M2 content is favorable for the solid-state luminescence of the
corresponding copolymers. Both the ΦF and the emission
enhancement (I90/I0 and A90/A0) of the copolymer gradually
increase as the M2 content increases.
Highly Luminescent Patterning of the Copolymers.
The generation of highly luminescent two-dimensional (2D)
patterning is important for the fabrication of optoelectronic
and biophotonic devices.61 Because the gel-like saturated
solutions of Pns exhibited highly efficient solid-state
luminescence and good solution processability, we tried the
possibility of patterning Pns to generate highly luminescent 2D
patterns with a well-ordered structure. Herein, high throughput
nanoimprint lithography was employed to fabricate the
luminescent 2D patterns.62 Taking P3 as an example, the
saturated solution of P3 in chloroform was first drop-casted
onto a clean silicon wafer. Then a poly(dimethylsiloxane)
(PDMS) template with the periodicity of 24 μm and feature
size of 12 μm was imprinted onto the drop-casting film. Finally,
the highly ordered 2D pattern was successfully achieved on the
substrate after evaporating the solvent and lifting off the
template. As shown in Figure 8a, the SEM image reveals that
imprinted pattern presents highly ordered line arrays with the
DOI: 10.1021/acs.macromol.9b00221
Macromolecules 2019, 52, 3668−3679
Macromolecules Article

Figure 7. (a, c) Emission spectra of P0 (a) and P3 (c) in THF and THF/water mixtures with varied water fractions (f w). (b, d) Plots of relative PL
intensity (I/I0) at 502 nm versus the composition of the aqueous mixtures of P0 (b) and Pns (d). Inset: fluorescence photos of P0 and P3 in THF
with a f w of 0 and 90% taken under 365 nm UV light irradiation. Solution concentration: 10−5 M; excitation wavelength: 365 nm.

Table 2. Fluorescent Properties of the Monomers and microscope. As depicted in Figure 8b, the fluorescence image
Polymersa shows obvious alternative bright and dark stripes with a high
contrast, and the scale of the stripes was in good consistence
I90/I0 A90/A0 Φsoln (%) Φsolid (%)
with that of the pattern as shown in SEM image. The bright
M1 13.6 8.7 ∼0 0 and dark stripes in this pattern can be readily assigned to the
M2 126.5 100.4 0.1 27.7 polymer and the blank space, respectively. This result
P0 5.0 4.5 ∼0 2.0 demonstrated that this kind of LLCPs could be used for the
P1 18.6 17.2 0.7 18.4 fabrication of highly luminescent 2D patterns.

■
P2 23.8 22.0 0.8 21.0
P3 25.3 23.0 1.1 24.3 CONCLUSIONS
a
Abbreviation: I90 and I0 = intensity at f w = 90% and 0%, respectively; In summary, highly luminescent monomer and LLCPs with the
A90 and A0 = the integral of the PL spectrum of samples at f w = 90% AIE effect were successfully prepared by rational molecular
and 0%, respectively; Φsoln and Φsolid = the fluorescent quantum yield
design. The obtained two monomers (M1 and M2) only
of the THF solution and solid powder of the samples, respectively.
differed in the presence of ester groups in their chemical
structures, but they showed significantly different photo-
same periodicity and feature size as the template. Meanwhile, physical behaviors. M1 with ester groups was almost
the morphology shows a perfect opposite pattern of the nonemissive due to the PET effect, while M2 without ester
corresponding template. Furthermore, the luminescence groups showed strong luminescence emission in solid state.
behavior of the pattern was investigated using a fluorescence After polymerization, all the obtained polymers showed typical
3676 DOI: 10.1021/acs.macromol.9b00221
Macromolecules 2019, 52, 3668−3679
Macromolecules
Figure 8. SEM image (a) and the fluorescence microscope image (b) of the regular line arrays of polymer P3 patterned on the Si substrate.
columnar liquid crystal phase (ColH) that was independent of
the chemical structure and component content. Meanwhile,
these polymers showed a typical AEE phenomenon. Although
the homopolymer P0 prepared from the radical homopolyme-
rization of M1 still showed weak solid-state emission, the
copolymers (P1−P3) prepared from the copolymerizations of
M2 and HCS were highly luminescent in the aggregated states.
The ΦF of the copolymers gradually increased (18.4, 21.0,
24.3%) with the increasing M2 content (18.0, 32.4, 45.1%) in
the copolymer structures. The obtained Pns was able to be
used for preparation of highly luminescent 2D patterns
through the nanoimprint lithography, indicating that this
kind of polymers were promising materials for applications in
optoelectronics, nanophotonics, and biological imaging and
sensing.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.macro-
mol.9b00221.
Materials; instruments and measurements; experiment
about some intermediate products; experiment results of
1 (6) Aldred, M. P.; Eastwood, A. J.; Kelly, S. M.; Vlachos, P.;
H NMR, variable-temperature 1D-WAXD, spectra
absorption spectra, emission spectra, molecular orbitals
of the ground states of the simplified P0 and P(M2)
(PDF)
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: xhl20040731@163.com (H.L.X.).
*E-mail: zqyu@szu.edu.cn (Z.Q.Y.).
*E-mail: tangbenz@ust.hk (B.Z.T.).
ORCID
He-Lou Xie: 0000-0003-4103-2634
Zhen-Qiang Yu: 0000-0002-0862-9415
Ben Zhong Tang: 0000-0002-0293-964X
Author Contributions
#
J.-C.Z. and T.H. contributed equally to this work.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was financially supported by National Natural
Science Foundation of China (NNSFC 21674088, 21374092,
3677
Article
and 21674065), Beijing National Laboratory for Molecular
Sciences (BNLMS201815), and the Hunan 2011 Collaborative
Innovation Center of Chemical Engineering & Technology
with Environmental Benignity and Effective Resource
Utilization.
■
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3679 DOI: 10.1021/acs.macromol.9b00221

Macromolecules 2019, 52, 3668−3679