Luminescent columnar liquid crystals based on AIE tetraphenylethylene with hydrazone groups bearing multiple alkyl chains

Article abstract of DOI:10.1016/j.dyepig.2018.07.018

A series of novel tetraphenylethylene aromatic acylhydrazone derivatives 11, 12 and 13 with 4, 8 or 12 alkyl chains were designed and synthesized in yields of 82–85%. Studies on the mesomorphic properties suggested the ordered hexagonal columnar mesophase

Full text of DOI:10.1016/j.dyepig.2018.07.018

Accepted Manuscript
Luminescent columnar liquid crystals based on AIE tetraphenylethylene with
hydrazone groups bearing multiple alkyl chains
Shengjie Jiang, Jiabin Qiu, Yunxiang Chen, Hongyu Guo, Fafu Yang
PII:
S0143-7208(18)31141-0
10.1016/j.dyepig.2018.07.018
DYPI 6872
DOI:
Reference:
To appear in: Dyes and Pigments
Received Date: 20 May 2018
Revised Date: 7 July 2018
Accepted Date: 10 July 2018
Please cite this article as: Jiang S, Qiu J, Chen Y, Guo H, Yang F, Luminescent columnar liquid crystals
based on AIE tetraphenylethylene with hydrazone groups bearing multiple alkyl chains, Dyes and
Pigments (2018), doi: 10.1016/j.dyepig.2018.07.018.
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ACCEPTED MANUSCRIPT
Luminescent columnar liquid crystals based on AIE tetraphenylethylene
with hydrazone groups bearing multiple alkyl chains
Shengjie Jiang,a Jiabin Qiu,a Yunxiang Chen,a Hongyu Guo,*a,b and Fafu Yang*a,c
5
aCollege of Chemistry and Chemical Engineering, Fujian Normal University, Fuzhou 350007, P. R.
China ;Tel: +0086-591-83465225; E-mail: yangfafu@fjnu.edu.cn
bFujian Key Laboratory of Polymer Materials, Fuzhou 350007, P. R. China
cFujian provincial Key Laboratory of Advanced Materials Oriented Chemical Engineering, Fuzhou
10 350007, P. R. China
A
series of novel tetraphenylethylene aromatic 30 Keywords: Tetraphenylethylene; Hydrazone; Fluorescence;
acylhydrazone derivatives 11, 12 and 13 with 4, 8 or 12 alkyl
chains were designed and synthesized in yields of 82-85%.
15 Studies on the mesomorphic properties suggested the ordered
hexagonal columnar mesophase for compounds 11, 12 and 13.
The increase in the number of alkyl chains was favourable for
decreasing the phase-transition temperatures and extending the
mesophase temperature range. Further, samples 11, 12 and 13
20 presented an excellent AIE effect. The fluorescence intensities
increased by 70, 84 and 43 times for samples 11, 12 and 13,
respectively. The absolute fluorescence quantum yields were
18.7%, 27.4% and 23.8% in solid films at room temperature
and 6.7%, 24.2% and 17.3% in the mesophase. These results
25 suggested that the number of alkyl chains greatly influenced
the fluorescence emission and sample 12 with 8 alkyl chains
exhibited the strongest fluorescence emission. Sample 12 also
displayed the electroluminescence performance on OLED
device.
Mesophase; Aggregation-induced emission
1. Introduction
Since the aggregation-induced emission (AIE) effect was
discovered by Tang’s group in 2001 [1-3], the AIE
35 luminogens have been studied widely and applied in various
research fields such as optoelectronic devices, chemical
sensors, solid-state dyes, fluorescence probes and bio-imaging
[4−15]. Especially, due to the excellent solid-state light-
emitting efficiency, the AIE-based multifunctional materials
40 exhibited great application potential in OLED devices [16-
18]. By decorating flexible chains on the AIE luminogens, the
so-called AIE liquid crystals could be prepared [19]. This kind
of luminescent liquid crystals had been paid considerable
attention because of the effective fusion of intrinsic
45 luminescent characteristic, the supramolecular organization
and self-healing properties within a mesophase [20, 21]. As a

result, some AIE liquid crystals based on AIE cores, such as
tetraphenylethylene with hydrazone groups bearing multiple
ACCEPTED MANUSCRIPT
tetraphenylethylene
and
diphenylacrylonitrile,
were
alkyl chains exhibited not only excellent AIE fluorescence
properties but also a good hexagonal columnar mesophase.
investigated and exhibited interesting AIE luminescent and
mesomorphic properties [22-40].
35 2. Experimental
2.1 General
5
Among all types of liquid crystals, columnar discotic
liquid crystals have attracted much commercial and academic
research interest over the years [41]. They possess unique
cores with π-π stacking structures, displaying high ordered
columnar mesophase with fast charge carrier mobility and
The chemical reagents were obtained from Aladdin Co. Ltd.
The inorganic reagents were used directly. The organic
solvents were purified by standard process before use. TLC
40 analysis was done on pre-coated glass plates. Silica gel (200-
300 mesh) was used for column chromatography. NMR
spectra were measured on a Bruker-ARX 400 instrument at 26
oC with tetramethylsilane (TMS) as internal standard. Mass
spectra were detected by Bruker mass spectrometer. UV-Vis
45 spectra were examined on Varian spectrometer. Fluorescence
spectra were measured in a conventional quartz cell
(10×10×45 nm) at 25oC on a Hitachi F-4500 spectrometer
equipped with a constant-temperature water bath. The
fluorescence absolute ΦF values were obtained on FLS920
50 Fluorescence spectrometer with a 6-inch integrating sphere.
POM (Leica DMRX) was obtained on a hot stage (Linkam
THMSE 600) to observe phase transitions. Thermal analysis
of the materials was carried out on DSC (Thermal Analysis
Q100). XRD data were obtained from SEIFERT-FPM
55 (XRD7) with Cu Kα 1.5406 Å as the radiation source under
40 kV, 30 mA power. The particle size and distribution were
measured by an ALV-5000 laser light scattering spectrometer
(DLS). Benzaldehyde derivatives 2, 4, 6 were synthesized by
10 extensive application prospects in organic field-effect
transistors, organic light-emitting diodes, organic photovoltaic
cells and gas sensors, etc [42-45]. Generally, the columnar
liquid crystals possessed symmetric and big coplanar aromatic
cores. However, the AIE luminogens are usually the
15 asymmetric and noncoplanar structures against effective π-π
packing in columnar mesophase, resulting in smectic or
nematic mesophases in most cases [22-40]. On the other hand,
it was well known that the hydrogen bond and the extended
aromatic structure were favourable for producing the
20 columnar mesophase [46-48], but these strategies were not
applied in columnar AIE liquid crystals up to now. In this
paper, in order to assure the columnar mesophase, the
hydrazone groups with NH groups and aromatic units bearing
multiple alkyl chains were successfully introduced on the
25 tetraphenylethylene core for the first time. The novel
columnar AIE liquid crystals were readily constructed based
on the positive influences of these hydrazone groups on
columnar mesophase. Moreover, the influences of different
numbers of alkyl chains (4, 8 and 12) on fluorescence
30 properties and mesomorphic properties were also first
investigated in detail. The results suggested that the
the
reported
procedures [49].
Tetraphenylethylene
60 tetrahydroxyl derivative 8 was prepared by reacting 2,4'-
dihydroxybenzophenone in Zn,TiCl4/THF system according
to the published literature [23].

9 as white powder in the yield of 75%. Tetraphenylethylene
ACCEPTED MANUSCRIPT
1
BrC12H25
tetraester derivative 9: H NMR (400 MHz, CDCl3) δppm:
HO
HO
CHO
CHO
C12H25
O
CHO
CH3CN / K2CO3
1
3
2
6.83 (d, J = 8.0 Hz, 8H, ArH), 6.54 (d, J = 8.0 Hz, 8H, ArH),
4.44 (s, 8H, OCH2), 4.14(q, 8H, OCH2), 1.17(t, J = 8.0 Hz,
20 12H, CH3); MALDI-TOF-MS (C42H44O12) Calcd. for m/z =
740.8, found: m/z = 740.7 (M+).
BrC12H25
C12H25
O
CHO
CH3CN / K2CO3
HO
HO
C12H25
C12H25
O
4
O
BrC12H25
HO
HO
CHO
C12H25
O
CHO
CH3CN / K2CO3
5
C12H25
O
6
OH
OCH2CO2Et
HO
OH
EtO2CH2CO
2.3
Synthesis of tetraphenylethylene tetraacylhydrazine
BrCH2CO2Et
K2CO3 / MeCN
TiCl4 / Zn / THF
O
derivative 10
OCH2CO2Et
9
HO
OH
EtO2CH2CO
OH
7
8
Tetraphenylethylene tetraester derivative 9 (0.740 g, 1 mmol)
25 and N2H4-H2O (1 mL) were refluxed in CHCl3/MeOH (V/V =
1:1(20 mL)) for 10 h. The TLC detection indicated that the
starting materials were consumed. The solvents were
evaporated under reduced pressure. The residue was
N2H4
H2N
HN
NH2
NH
O
O
O
O
O
O
NH
NH2
HN
10
O
O
H2N
recrystallized in CHCl3/MeOH (V/V
= 1:3) to give
2 (4 or 6)
R3
R2
R1
R2
R3
C
N
N
C
O
H
O
30 tetraphenylethylene tetraacylhydrazine derivative 10 as white
powder in the yield of 90%. Tetraphenylethylene
tetraacylhydrazine derivative 10: 1H NMR (400 MHz,
DMSO) δppm: 9.32 (s, 4H, NH), 6.84 (d, J = 8.0 Hz, 8H,
ArH), 6.72 (d, J = 8.0 Hz, 8H, ArH), 4.39 (s, 8H, OCH2),
35 4.31(bs, 8H, NH2); MALDI-TOF-MS (C34H36N8O8) Calcd.for
m/z = 684.3, found: m/z = 684.3 (M+).
H
HN
NH
R1
O
O
11: R1 = R3 = H, R2 = -OC12H25
12: R1 = H, R2 = R3 = -OC12H25
13: R1 = R2 = R3 = -OC12H25
O
R1
R2
R3
O
R3
R2
NH
HN
N
H
H
O
N C
O
C
R1
Scheme 1 The synthetic route of compounds 11, 12 and 13
5
2.2. Synthesis of tetraphenylethylene tetraester derivative 9
Tetrahydroxy-tetraphenylethylene 8 (0.396 g, 1 mmol),
anhydrous potassium carbonate (5.0 g, 36.2 mmol) and ethyl
bromoroacetate (2.0 mL) were added in dried acetonitrile
(40mL). After refluxing and stirring overnight, the TLC
2.4 Synthesis of target tetraphenylethylene tetrahydrazone
derivative 11, 12 and 13
The mixture of tetraphenylethylene tetraacylhydrazine
40 derivative 10 (0.342 g, 0.5 mmol) and benzaldehyde
derivative 2 (4 or 6) (2 mmol) were refluxed in 20 mL of
CHCl3/MeOH (V/V = 2:1) for 12 h with three drops of glacial
acetic acid as catalysts. After reaction, the solvents was
evaporated under reduced pressure and the residue was
45 recrystallized in CHCl3/MeOH (V/V = 1:5) for three times.
Only one dot was found on TLC plate under various solvents,
indicating the good purification for product. Compounds 11,
12 and 13 were obtained as white powder in the yields of 82%,
84% and 85%, respectively. Compound 11: FT-IR (KBr, cm-1):
10 detection suggested that the starting material almost
disappeared completely. After reaction, HCl solution (50 mL,
1 M) was dropped in reaction system, and the mixture was
extracted with CHCl3 (50 mL). The organic phase was
separated and concentrated. The residue was recrystallized in
15 CHCl3/MeOH to give tetraphenylethylene tetraester derivative

1
2923, 2853, 1681, 1602, 1508, 1269, 1177, 808. H NMR
As discussed above, the tetraphenylethylene aromatic
acylhydrazone derivatives 11, 12 and 13 were designed as
target compounds due to the feature that the extended
ACCEPTED MANUSCRIPT
(400 MHz, CDCl3) δppm: 1H NMR (400 MHz, CDCl3) δppm:
9.39 (bs, 4H, NH), 8.13 (s, 4H, CH), 7.71 (d, J = 8.0 Hz, 8H,
ArH), 6.91-7.02 (m, 16H, ArH), 6.72 (d, J = 8.0 Hz, 8H,
5
ArH), 4.61 (s, 8H, OCH2), 3.99 (s, 8H, OCH2), 4.14(q, 8H, 45 aromatic acylhydrazone structure and the hydrogen bond of
OCH2), 0.85-1.80 (m, 92H, C11H23); 13C NMR (100 MHz,
NH group were favourable for columnar mesophase. The
CDCl3) δppm: 164.37, 155.64, 148.34, 140.37, 132.40, 131.66,
different numbers of peripheral alkyl chains (4, 8 and 12)
129.67, 125.70, 114.68, 114.01, 105.06, 68.13, 67.03, 31.92,
29.64, 29.58, 29.41, 29.19, 29.06, 26.02, 25.96, 22.63, 14.11;
were decorated on hydrazone groups to investigate the
influence of multiple alkyl chains on fluorescence properties
50 and mesomorphic properties. The synthetic routes to the target
compounds 11, 12 and 13 were illustrated in Scheme 1. Firstly,
by reacting 1-bromododecane with 4-hydroxy benzaldehyde,
3,4-dihydroxybenzaldehyde or 2,3,4-trihydroxybenzaldehyde
in K2CO3/MeCN system [46], compounds 2, 4 and 6 were
55 conveniently prepared in yields of 86%, 88% and 80%,
respectively. On the other hand, according to the literature
method [23], tetraphenylethylene tetrahydroxyl derivative 8
was synthesized by reacting 2,4'-dihydroxybenzophenone in
Zn,TiCl4/THF system in yield of 88%. Further, the
10 MALDI-TOF-MS (C110H148N8O12) Calcd. for m/z = 1774.4,
found: m/z = 1774.0 (M+), 1797.1 (MNa+). HR-MS(ESI)
(C110H148N8O12) [M+Na]+: Calcd.: 1797.1148. found:
1797.0751(M+Na)+. Anal. calcd. for C110H148N8O12: C, 74.46;
H, 8.41; N, 6.32. found: C, 74.51; H, 8.48; N, 6.21.
15 Compound 12: FT-IR (KBr, cm-1): 2923, 2853, 1681, 1602,
1
1508, 1269, 1177, 808. H NMR (400 MHz, CDCl3) δppm:
9.48 (bs, 4H, NH), 8.11 (s, 4H, CH), 7.45 (s, 4H, ArH), 7.10
(d, J = 8.0 Hz, 4H, ArH), 6.84-6.97 (m, 12H, ArH), 6.71 (d, J
= 8.0 Hz, 8H, ArH), 4.60 (s, 8H, OCH2), 4.00-4.05 (m, 16H,
20 OCH2), 0.85-1.84 (m, 184H, C11H23); 13C NMR (100 MHz,
CDCl3) δppm: 164.16, 155.55, 151.72, 150.09, 149.45, 145.54,
132.77, 125.79, 123.07, 121.66, 114.07, 112.34, 110.54, 69.25,
69.04, 67.07, 31.94, 29.68, 29.49, 29.45, 29.39, 29.28, 29.17,
26.04, 22.71, 14.13; MALDI-TOF-MS (C158H244N8O16) Calcd.
25 for m/z = 2511.6, found: m/z = 2511.6 (M+). Anal. calcd. for 60 tetraphenylethylene derivative 9 was prepared in the yield of
C158H244N8O16: C, 75.55; H, 9.79; N, 4.46. found: C, 75.61; H,
9.73; N, 4.38. Compound 13: FT-IR (KBr, cm-1): 2924, 2853,
75% by reacting compound 8 with ethyl bromoacetate in
K2CO3/MeCN system. After the aminolysis reaction of
1
1684, 1593, 1502, 1297, 1180, 803. H NMR (400 MHz,
CDCl3) δppm: 9.36 (bs, 4H, NH), 8.38 (s, 4H, CH), 7.01 (d, J
30 = 8.0 Hz, 8H, ArH), 6.68-6.76 (m, 16H, ArH), 4.61 (s, 8H,
OCH2), 3.95-4.10 (m, 24H, OCH2), 0.86-1.86 (m, 276H,
C11H23); 13C NMR (100 MHz, CDCl3) δppm: 164.09, 155.88,
152.76, 145.62, 141.13, 132.83, 132.44, 124.35, 121.81,
113.95, 108.59, 74.75, 73.53, 68.80, 31.93, 30.32, 30.21,
35 29.66, 29.36, 29.31, 26.15, 26.11, 22.69, 14.10; MALDI-
TOF-MS(C206H340N8O20) Calcd.for m/z = 3248.9, found: m/z =
3247.6 (M+). Anal. calcd. for C206H340N8O20: C, 76.15;
H,10.55; N, 3.45. found: C, 76.10; H, 10.62; N,3.38.
compound 9 with N2H4, the tetraphenylethylene hydrazide
derivative 10 was obtained in yield of 90%. Finally, based on
65 the Schiff-base condensation, the target tetraphenylethylene
hydrazone derivatives 11, 12 and 13 were prepared by
refluxing compound 10 with compounds 2, 4 and 6 in CHCl3 /
MeOH (1: 5, V/V) system. The purification process was
simple with recrystallization due to the high reaction
70 efficiency of Schiff-base condensation and the yields were as
high as 82%, 84% and 85%, respectively. The structures of
the new compounds were characterized by FT-IR
40 3. Results and discussion
3.1. Synthesis and characterization

1
spectrometry, H and 13C NMR spectroscopy, MALDI-TOF
The phase transition behavior of compounds 11, 12 and 13
ACCEPTED MANUSCRIPT
mass spectrometry and elemental analysis (see SI). All the 20 were firstly investigated by differential scanning calorimetry
characterization data were in accordance with their structures.
(DSC) under a nitrogen blanket at a scan rate of 10 °C / min.
The DSC curves and the corresponding phase transition
temperatures and enthalpy changes were shown in Figure 1
and Table 1, respectively. It was observed that compound 11
1
For example, a pair of doublet in H NMR spectra was
5
observed for the tetraphenylethylene skeleton, indicating the
symmetric tetra-substituted structure for these new
compounds.
o
o
25 exhibited two endothermic peaks at 137.8 C and 164.9 C on
o
heating and two exothermic peaks at 133.7 oC and 162.6 C
3.2. Mesomorphic properties
upon cooling, respectively. Compound 12 also had two
o
o
endothermic peaks at 108.9 C and 181.3 C for the heating
process and two exothermic peaks at 99.9 oC and 177.1 oC for
30 the cooling process. Compound 13 exhibited broad thermic
cooling
heating
6
4
13
o
o
2
12
11
peaks at low temperatures at 36.1 C on heating and 34.7 C
cooling
heating
on cooling, and a small thermic peak at 152.6 oC for heating
0
o
cooling
process and 141.6 C for cooling process, respectively. These
-2
heating
250
results certainly implied the reversible phase transition for
35 compounds 11, 12 and 13 with the crystal phase-mesophase-
isotropic phase process. Moreover, one can see that the
melting points of compounds 11, 12 and 13 presented the
-50
0
50
100
150
200
Temperature (oC)
10
Figure 1 The DSC traces of compounds 11, 12 and 13 for
cooling and second heating at a rate of 10 oC / min.
o
o
orderly change of 11 (137.8 C) > 12 (108.9 C) > 13 (36.1
oC). After calculation, the mesophase temperature ranges of
40 compounds 11, 12 and 13 also displayed the orderly changes
15 Table 1 Transition temperatures (oC) and enthalpy changes
(kJ/mol) of compounds 11, 12 and 13
o
o
o
of 11 (27.1 C) < 12 (72.4 C) < 13 (116.5 C). These results
were in accordance with the order of the number of alkyl
chains of 11 (4 chains) < 12 (8 chains) < 13 (12 chains),
suggesting that the multiple alkyl chains influenced greatly
45 the mesomorphic behavior. The more peripheral alkyl chains
were favourable for decreasing the phase-transition
temperatures and extending the mesophase temperature range.
The broad peaks and obvious hysteresis phenomena for
compound 13 on thermic process could be attributed to this
compound Phase
Heating scan
Cooling scan
T(∆H)
transition[a] T(∆H)
11
12
13
Cr-Col
137.8(18.5)
164.9(1.8)
108.9(20.3)
181.3(3.3)
36.1(19.8)
152.6(1.2)
133.7(22.6)
162.6(2.1)
99.9(18.9)
177.1(2.6)
34.7(18.6)
141.6(1.3)
Col-Iso
Cr-Colh
Colh-Iso
Cr-Colh
Colh-Iso
[a] Cr=crystalline, Colh=hexagonal columnar mesophase,
Iso=isotropic.

kind of viscous material with 12 long alkyl chains. Based on
weak reflections at 2.46o, 4.26o, 5.92o and 2.24o, 3.88o, 4.48o,
ACCEPTED MANUSCRIPT
these DSC data, it could be summarized that compounds 11, 30 respectively. Based on the Bragg equation d = 1.5406/(2sinθ),
12 and 13 possessed good liquid crystalline behavior, and the
more alkyl chains contributed to decrease the phase-transition
temperatures and extend the mesophase temperature ranges.
The mesomorphic textures of compounds 11, 12 and 13
the corresponding distances for these reflections were
calculated as 32.80 Å, 18.91 Å, 16.39 Å for sample 11, 35.88
Å, 20.71 Å, 17.94 Å for sample 12, and 39.40 Å, 22.75 Å,
19.71 Å for sample 13. These data were in agreement with the
5
were further observed by using polarising optical microscopy 35 ratios of 1:1/√3:1/√4, suggesting the [d100], [d110] and [d200
]
(POM). Upon heating and cooling process, the phase
transitions of Cr-Col and Col-Iso phase were distinguished
reflections for hexagonal columnar liquid crystals. In the
wide-region, the broad halos at 2θ = 15~30o could be
attributed to the reflections of the molten alkyl chains. A
small reflection at 21.38o for sample 11, 21.80o for sample 12,
10 clearly. Their phase transition temperatures were
approximately in accordance with the thermic peaks of DSC
curves. During slowly cooling form the isotropic phase, the 40 20.94o for sample 13 could be observed. These reflections
mesophase textures can be observed as shown in Figure 2. All
of them exhibited the orderly textures, which could be seen as
15 the type of pseudo-confocal conic texture for columnar
mesophase. This proposal was further supported by XRD
analysis.
suggested the distances of 4.15 Å for sample 11, 4.07 Å
sample 12 and 4.24 Å sample 13, which corresponded to the
intracolumnar distances of π-π interaction for the ordered
hexagonal columnar liquid crystal. Moreover, the lattice
45 parameter (ɑ) for samples 11, 12 and 13 could be calculated as
37.82 Å, 41.44 Å and 45.50 Å, respectively. These data were
smaller than the diameter of samples 11, 12 and 13 (~60 Å)
estimated by the CPK molecular model. These results might
suggest that the soft alkyl chains for these samples adopted
50 the folding conformation and/or the interdigitation in the
neighbouring columns. Thus, the possible molecular stacking
of hexagonal columns for these samples could be proposed in
Figure 3 (using sample 13 as representative one). Based on all
the analyses of DSC, POM and XRD results, it could be
55 concluded that samples 11, 12 and 13 possessed the ordered
hexagonal columnar mesophase. The more alkyl chains
resulted in the lower phase-transition temperatures and wider
mesophase temperature scopes.
Figure 2 The POM textures of compounds 11, 12 and 13
o
o
o
20 upon cooling at 150 C for 11, 120 C for 12, 60 C for 13
(Zooming in 200 times)
The XRD analyses for mesophase were carried out at the
liquid crystalline phase of samples 11, 12 and 13. The
25 corresponding XRD curves were illustrated in Figure 3. In the
small-angle region, sample 11 exhibited two strong reflections
and one weak reflection at 2.69o, 4.67o and 5.39o, respectively.
Samples 12 and 13 showed one strong reflection and two

of 67000 (a.u.). On the other hand, the data in Figure 5
ACCEPTED MANUSCRIPT
4.67o
2.69o
800
700
600
500
400
300
200
100
0
indicated that, compared with the fluorescence in pure THF
solutions, the fluorescence intensities of samples 11, 12 and
35 13 increased by 70, 84 and 43 times in THF/H2O mixtures
with 95% of H2O fractions, respectively. All these results
suggested that the multiple alkyl chains influenced on the AIE
effect obviously and the sample 12 with eight alkyl chains
presented the strong AIE effect. The hydrodynamic size
40 distribution of compounds 11, 12 and 13 in solution of
H2O/THF (5:95) was also evaluated by dynamic light
scattering (DLS). The results showed that the hydrodynamic
average size distribution of the compounds 11, 12 and 13
were 254 nm, 400 nm and 600 nm, which increased orderly
45 with the increase of number of alkyl chains. These phenomena
could be explained by that the multiple alkyl chains decreased
dramatically the solubility in H2O/THF solution and enhanced
the aggregation abilities.
O
O
O
C
O
NH
O
O
O
O
O
CN
N
O
H
O
O
O
O
C
N
NC
O
NH
H
HN
H
O
O
HN
H
O
O
O
H
C
O
H
O
NH
O N
O
H
HN
H
O
O
O
O
NH
CN
O
HN
O
O
O
NC
O
O
CNO
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
NC
O
C
N
O
O
O
NC
O
NH
H
O
O
C
N
N
C
HN
H
O
C
N
O
O
O
O
O
O
NH
H
O
O
HN
H
NH
HN
H
O
O
H
O
O
H
H
O
NH
O N
O
HN
H
NH
O NC
H
O
H
O
O
O
H
O
O
C
O
NH
C
N
O
HN
HN
O
O
O
C
N
O
O
N
C
O
O
C
N
O
O
O
O
O
O
O
O
O
O
O
¨»
O
2.24o
2.46o
O
O
O
O
O
O
O
C
O
NH
H
O
C
N
N
C
O
NH
H
O
O
O
C
N
N
HN
H
O
O
HN
H
O
O
O
O
H
H
C
O
O
H
HN
NH
O N
H
O
O
NH
O
N
O
HN
C
N
O
O
C
N
O
C
O
O
O
O
O
O
O
O
O
O
5
21.38o
d
100
5.39o
d
110
11
12
4.26o
4.92o
21.80o
20.94o
3.88o
4.48o
13
10
20
30
40
Degree (2
θ)
0
o
10 Figure 3 XRD traces tested at 150 C for 11, 120 C for 12
o
and 60 C for 13, and the proposed molecular stacking model
for hexagonal columnar mesophase of compound 13.
3.3. photophysical properties
15
TPE is a well-known aggregation induced emission
luminogen (AIEgen). To investigate the fluorescence
properties of samples 11, 12 and 13, their UV-vis spectra and
the fluorescence spectra in THF and THF / water mixtures
were measured. Compounds 11, 12 and 13 showed similar
11
60000
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
95%
50000
40000
30000
20000
10000
0
20 UV-vis signals with absorption at 300-350 nm and
fluorescence emission at 400-600 nm based on the same TPE
cores. The fluorescence changes in different THF / water
mixtures are presented in Figure 4 and the comparison
changes for fluorescences (I/I0) were summarised in Figure 5.
25 As shown in Fig 4, the fluorescence spectra clearly showed
the enhancement with the increase of H2O fractions in
THF/H2O mixtures. Samples 11, 12 and 13 almost did not
emit in pure THF solution. But fluorescence gradually became
stronger when the H2O fractions > 30%, reaching their
30 maximum emission at 95%. One can see that sample 12
exhibited the strongest fluorescence at 95% with the intensity
THF THF/H2O(5:95)
400
450
500
550
600
650
700
750
Wavelength (nm)
12
70000
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
95%
60000
50000
40000
30000
20000
10000
0
THF THF/H2O(5:95)
400
450
500
550
600
650
700
750
Wavelength (nm)
50

ACCEPTED MANUSCRIPT
13
11
40000
30000
20000
10000
0
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
95%
THF THF/H2O(5:95)
400
450
500
550
600
650
700
750
Wavelength (nm)
200
400
600
800
1000
Figure 4 The fluorescence spectra of samples 11, 12 and 13 in
THF/H2O mixtures with different fractions of H2O (1×10-5 M)
excited at λ = 320 nm. (Their pictures in pure THF and
THF/H2O (5:95) solutions were inserted).
Diameter (nm)
5
12
90
11
12
13
80
70
60
50
40
30
20
10
0
0
400
800
Diameter (nm)
1200
1600
2000
-10
0
20
40
60
80
100
20
f
(vol%)
w
Figure 5 The ratio variation (I/I0) for fluorescence intensities
of samples 11, 12 and 13 with the changes of fractions of H2O
13
10 in THF/H2O mixtures.
15
0
400
800
1200
1600
2000
Diameter (nm)
Figure 6 Hydrodynamic size distribution of samples 11, 12
and 13 (1×10-5 M) based on DLS measurements in solution of
25 H2O/THF (5:95).

the strong AIE effect, leading to strong fluorescence in solid
ACCEPTED MANUSCRIPT
70000
60000
50000
40000
30000
20000
10000
0
12 before heating
12 after heating
films. On the other hand, the multiple alkyl chains were also
favourable for the orderly π-π stacking for TPE cores,
producing the ACQ effect and resulting in the red shift and
30 decrease of fluorescence. Nevertheless, sample 12 with 8
alkyl chains still displayed strong fluorescence with good
fluorescence quantum yields at both room temperature and
mesophase temperature.
13 before heating
13 after heating
11 before heating
11 after heating
400
450
500
550
600
650
700
750
800
wavelength / nm
Figure 7 The fluorescence spectra (λex = 320 nm) of solid
films of samples 11, 12 and 13 before and after heating at
mesophase temperatures (150 0C for 11, 120 oC for 12 and 50
oC for 13). (Their pictures before and after heating for 12 were
inserted)
5
LUMO 5.582 eV
LUMO 5.579 eV
LUMO 5.597 eV
∆E
11.390 eV
∆E
11.393 eV
∆E
11.406 eV
HOMO -5.808 eV
HOMO -5.814 eV
HOMO -5.809 eV
Furthermore, the fluorescence behavior of samples 11, 12
and 13 in solid films at room temperature and mesophase
10 were investigated. Figure 7 illustrated the fluorescence spectra
of samples 11, 12 and 13 before and after heating the
mesophase. It can be seen that, compared with the
fluorescence spectra in solution (Figure 4), no obvious red
shift or blue shift occurred. Samples 11, 12 and 13 exhibited
15 strong fluorescence in solid films. The absolute fluorescence
quantum yields of samples 11, 12 and 13 in solid films were
as high as 18.7%, 27.4% and 23.8%, respectively. Also, the
fluorescence spectra of samples 11, 12 and 13 in the
mesophase showed some red shifts in comparison with that
20 before heating. The fluorescence intensities also decreased a
little after heating with the absolute fluorescence quantum
yields of 6.7%, 24.2% and 17.3% for samples 11, 12 and 13,
respectively. These results suggested that the numbers of alkyl
chains influenced greatly on fluorescence quantum yields. The
25 alkyl chains could enhance the steric hindrance and produce
13
12
11
35 Figure 8 Molecular theoretical orbital amplitude plots of
HOMO and LUMO energy levels of compounds 11, 12 and
13
In order to further study the relationship of structures and
40 properties, a density functional theory (DFT) calculation to
better understand geometry and electronics through the
Gaussian 03 program was performed. The optimized
geometry and space diagrams for the highest occupied
molecular orbital (HOMO) and the lowest unoccupied
45 molecular orbital (LUMO) were shown in Figure 8. It can be
seen that the orbital electrons of the molecule were mainly
distributed on the plane of the conjugated skeleton of the TPE
nucleus, indicating that the charge transfer between
tetraphenylethylene unit and hydrazone groups was very weak

and was consistent with its lower absorbance wavelength.
performance including brightness and efficiency, this
electroluminescence performance certainly suggested that this
kind of AIE liquid crystal possessed the potential application
ACCEPTED MANUSCRIPT
Compounds 11, 12 and 13 presented similar electron cloud
distributions in their HOMO and LUMO orbitals, which were
in agreement with their similar UV and fluorescence spectra 35 prospect for OLED device.
5
based
on
their
similar
aromatic
conjugated
Table 2 Electroluminescent performance data of OLEDsa
Vonsetb (V) Lmaxc (cd m-2) ηc,d(cd A-1) ηp,d(Im W-1) λeme (nm)
f
）
CIE（
，
x
y
tetraphenylethylene skeleton.
14
4.541
3.898
0.0095
582
0.4338, 0.4277
3.4 Electroluminescence properties
aDevice configuration: ITO / PEDOT / emissive layer / TPBI
As sample 12 exhibited the strongest fluorescence emission,
b
(20nm) LiF（10nm）/ Al（100nm） Vonset: turn-on voltage
10 the electroluminescence (EL) performance of sample 12 as
representative one was investigated in an OLED device.
Sample 12 was employed as the emitter with the configuration
of ITO / PEDOT / emissive layer (~40 nm) / TPBI (20 nm)
LiF (10 nm) / Al (100 nm). The key device performance data
15 were summarized in Table 2. Figures 9 (a-b) depicted the
current density-voltage-luminance (J-V-L) characteristics of
the OLED produced. The OLED of the device showed a high
driving voltage of 14V (Vonset, equivalent to 1 cdm-2)
probably due to the unbalanced charge carrier mobility in
20 these devices. A low luminance (Lmax) of 4.54 cdm-2 for
current efficiency (ηc) was 3.898 cd A-1, and the power
efficiency (ηp) was 0.0059 lmW-1. The steady-state EL
spectrum of the device at a driving voltage of 15 V (Figure
9c) showed an emission peak at 582 nm. The device exhibited
25 excellent spectral stability over a wide range of operating
voltages (Figure 9d). The EL spectrum of the device at 15V
was used to determine the CIE chromaticity coordinates.
International Commission on Illumination (CIE) color
coordinates was shown in Figure 9e. The CIE coordinates
30 (0.4338, 0.4277) listed in Table 2 correspond to bright yellow
emission. Although this device was not optimized for better
c
d
at luminance of 1 cd m-2. Lmax: luminance at 20 V. Current
e
40 efficiency( ηc), power efficiency (ηp). λem: emission
wavelength maximum at 15 V. fCIE color coordinate.
60
(a)
50
40
30
20
10
0
0
5
10
15
20
25
Valtage£¨V£©
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
(b)
14
16
18
20
22
24
Voltage£¨V£©

4. Conclusion
ACCEPTED MANUSCRIPT
0.6
0.4
0.2
0.0
(c)
10 In summary, three novel tetraphenylethylene aromatic
acylhydrazone derivatives 11, 12 and 13 with 4, 8 or 12 alkyl
chains were designed and synthesized in 82-85% yields. Their
structures were confirmed by FT-IR spectrometry, H and 13C
1
NMR spectroscopy, MALDI-TOF mass spectrometry and
15 elemental analysis. The mesomorphic properties were
investigated by DSC, POM and XRD analysis, suggesting
they had the ordered hexagonal columnar mesophase. The
more alkyl chains contributed to decrease the phase-transition
temperatures and extend the mesophase range of the mesophase.
20 The studies on photophysical properties implied that
compounds 11, 12 and 13 exhibited the excellent AIE effects
and the fluorescence intensities increased by 70, 84 and 43
times for samples 11, 12 and 13, respectively. Compounds 11,
12 and 13 also showed good fluorescence with moderate
25 absolute fluorescence quantum yields in solid films at room
temperature and mesophase temperature. The absolute
fluorescence quantum yields of sample 12 were as high as
27.4% in solid film at room temperature and 24.2% in the
mesophase. The OLED test suggested that sample 12
30 possessed the electroluminescence properties, indicating the
potential application prospect of these novel AIE liquid
crystals in the field of OLED device.
300
400
500
600
700
800
Wavelength(nm)
0.6
0.4
0.2
0.0
(d)
5V
10V
15V
20V
300
400
500
Wavelength (nm)
600
700
800
Acknowledgment. Financial support from the National
35 Natural Science Foundation of China (No: 21406036), Fujian
Natural Science Foundation of China (No. 2017J01571) and
the National Undergraduate Innovation Program in Fujian
Normal University were greatly acknowledged.
Figure 9 (a-b) J-V-L characteristics, (c) PL spectra (inset) and
EL spectra of OLED device, (d) EL spectra of device at
different bias voltages and (e) CIE coordinates of the OLED.
5

[10] Yuan Y, Zhang CJ, Gao M, Zhang R, Tang BZ, Liu B.
ACCEPTED MANUSCRIPT
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ACCEPTED MANUSCRIPT
Novel tetraphenylethylene acylhydrazone derivatives 11, 12 and 13 were prepared.
Compounds 11, 12 and 13 possess hexagonal columnar mesophases.
Compounds 11, 12 and 13 presented excellent AIE effect.
The number of alkyl chains influences the mesophase and fluorescence emission.
Sample 12 displayed the electroluminescence performance on OLED device.