New cyano-substituted organic dyes containing different electrophilic groups: Aggregation-induced emission and large two-photon absorption cross section

Article abstract of DOI:10.1016/j.tet.2014.05.016

Three aggregation-induced emission active dyes (3a-c) were synthesized and their one- and twophoton absorption properties have been investigated. They were all found to be weakly fluorescent in THF solution, while they exhibited dramatic fluorescence enhancement in water/THF mixtures. The solid fluorescence of 3a-c was recorded and their fluorescence quantum efficiency (φ_f) values were determined to be 8.0%, 8.1%, and 16.4%, respectively. Moreover, the two-photon absorption (2PA) crosssections (σ) of 3a-c were measured and 3a showed the highest value of 702 GM The excellent aggregation-induced emission and 2PA properties provide a promising alternative for biophotonic materials.

Full text of DOI:10.1016/j.tet.2014.05.016

Accepted Manuscript
New cyano-substituted organic dyes containing different electrophilic groups:
aggregation-induced emission and large two-photon absorption cross section
Haitao Zhou , Wei Huang , Li Ding , Shengyun Cai , Xin Li , Bo Li , Jianhua Su
PII:
S0040-4020(14)00676-0
10.1016/j.tet.2014.05.016
TET 25565
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 6 March 2014
Revised Date: 26 April 2014
Accepted Date: 5 May 2014
Please cite this article as: Zhou H, Huang W, Ding L, Cai S, Li X, Li B, Su J, New cyano-substituted
organic dyes containing different electrophilic groups: aggregation-induced emission and large two-
photon absorption cross section, Tetrahedron (2014), doi: 10.1016/j.tet.2014.05.016.
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New cyano-substituted organic dyes containing
different electrophilic groups: aggregation-
induced emission and large two-photon
absorption cross section
Leave this area blank for abstract info.
Haitao Zhou a, Wei Huang a, Li Ding a, Shengyun Cai a, Xin Li b, Bo Li c and Jianhua Su a
a
Key Laboratory for Advanced Materials and Institute of Fine Chemicals, East China University of Science &
Technology, Shanghai 200237, P.R. China.
b
Department of Theoretical Chemistry and Biology, School of Biotechnology, KTH Royal Institute of
Technology, Stockholm SE-10691, Sweden.
c Key Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shang
hai 200241, P.R. China.

1
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Tetrahedron
journal homepage: www.elsevier.com
New cyano-substituted organic dyes containing different electrophilic groups:
aggregation-induced emission and large two-photon absorption cross section
Haitao Zhou a, Wei Huang a, Li Ding a, Shengyun Cai a, Xin Li b, Bo Li c and Jianhua Su a
a Key Laboratory for Advanced Materials and Institute of Fine Chemicals, East China University of Science & Technology, Shanghai 200237, P.R. China.
b Department of Theoretical Chemistry and Biology, School of Biotechnology, KTH Royal Institute of Technology, Stockholm SE-10691, Sweden.
c Key Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai 200241, P.R. China.
ARTICLE INFO
ABSTRACT
Three aggregation-induced emission active dyes (3a-3c) were synthesized and their one- and
two-photon absorption properties have been investigated. They were all found to be weakly
fluorescent in THF solution, while they exhibited dramatic fluorescence enhancement in
water/THF mixtures. The solid fluorescence of 3a-3c was recorded and their fluorescence
quantum efficiency (ΦF) values were determined to be 8.0 %, 8.1 % and 16.4 %, respectively.
Article history:
Received
Received in revised form
Accepted
Available online
Moreover, the two-photon absorption (2PA) cross-sections (σ) of 3a-3c were measured and 3a
showed a highest value of 702 GM. The excellent aggregation-induced emission and 2PA
properties provide a promising alternative for biophotonic materials.
Keywords:
Aggregation-induced emission
Two photon absorption
Cross section
2009 Elsevier Ltd. All rights reserved
.
Solid fluorescence
1. Introduction
extend the conjugation chain. In view of this, three new type D-
π-A-π-D cyano-substituted dyes 3a-3c (shown in Scheme 1) with
triphenylamine as electron-donating group, 3,6-diphenylpyrrolo-
[3,4-c]pyrrole-1,4(2H,5H)-dione (A1), benzothiadiazole (A2) or
benzotriazole (A3) as acceptors, respectively, were synthesized.
All the dyes were designed according to the following
considerations: 1) A1, A2 and A3 are common electron
withdrawing groups. A1 exhibits strong fluorescence and are
currently some of the most popular building blocks in
luminescence-based studies due to its superb optoelectronic
performance.8 A2 has shown good performance in organic
electronic devices because of its strong electron-withdrawing
ability and the existence of heteroatom interactions.9 A3 is a
known acceptor which provides an alkylation position to improve
solubility, and was commonly employed in conjugated polymers,
but it is rarely introduced to 2PA or AIE materials.10 Thus, we
employ these acceptors as building blocks in our study and to
investigate the effect of electron-withdrawing strength on 2PA σ
value of the dyes; 2) Triphenylamine and carbazole have been
widely used in optoelectronic materials. Compared with
carbazole, triphenylamine is stronger in electron donating ability
and less planar in conformation. So we prefer to employ
triphenylamine as the electron donating group; 3) Cyano-
substituted dyes showed good optical and electrical properties
due to their high electron affinities. Molecules including an
electron-withdrawing cyano-group on the central phenylene ring
exhibit strong fluorescence and high 2PA σ values.11 As a
consequence, owing to the good optoelectronic properties of
triphenylamine and the acceptors, 3a-3c are expected to exhibit
large 2PA σ values, as well as good AIE properties.
Organic materials displaying two-photon absorption (2PA)
have drawn a great many research attentions due to their potential
applications in photoelectric devices. So far, much effort has
been devoted to designing molecules with large 2PA cross
section (σ) and many dyes with large σ value have been
reported.1 However, most of the dyes are hydrophobic and they
generally show significant fluorescence quenching caused by
aggregation, hence these disadvantages extremely limit their
applications, especially in solid-state devices and biological
imaging.2 Encouragingly, the discovery of aggregation induced
emission (AIE) by Tang and co-workers opened up a new
approach for us.3 On account of this, 2PA dyes with AIE effect
have been widely studied.
In our previous study, we synthetized several cyano-
substituted 2PA dyes with multibranched diphenylamines or
carbazoles as electron donor.4 Owing to the desirable electron-
donating and hole transporting capabilities of diphenylamine and
carbazole,5 as well as the high electron affinity of cyano-group,
these dyes show good 2PA and AIE properties. Nevertheless, the
relatively low σ value became a drawback. Studies showed that
the enhancement of σ value is related to intramolecular charge
transfer (ICT) from the terminal donor groups to the π-bridge.6
Furthermore, extension of the conjugation chain, introduction of
a strong acceptor or donor group into the π-bridge and
appropriate choice of solvent polarity could also result in large σ
values.7 Herein, we optimize our design by introducing an
electron-withdrawing group in the central core of the dye to
———
Corresponding author. Tel.: +86 21 6425-2288; fax: +86 21 6425-2288; e-mail: bbsjh@ecust.edu.cn

2
Tetrahedron
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2. Results and Discussion
2.1. Synthesis
The detailed synthetic routes of three compounds 3a-3c was
described in Scheme 2. The key intermediate, bis(4-(diphenyl-
amino)phenyl)methanone (I2), was synthesized according to
previous literature.12 The target compounds 3a-3c were
synthesized by Suzuki coupling reaction between 2a-2c and I3,
which is the boron compound of I2, in the presence of a
1
palladium catalyst, and confirmed by H NMR, 13C NMR and
mass spectroscopy (MS).
Fig. 1. One-photon absorption spectra of 3a-3c in THF.
2.3. Solvent effect
The solvent effect is usually observed in dyes containing D-A
pairs. To investigate the effects of solvent polarity on the opitical
properties of the dyes, the emission spectra of 3a-3c in different
solvents were recorded by increasing the polarity from
cyclohexane to ethanol (Fig. 3d-e). All the dyes undergo a
bathochromic shift as the polarity increases. These results
indicate that a significant ICT effect occurs in these dyes.
2.4. AIE properties
Dyes 3a-3c are well soluble in common organic solvents such
as THF and dichloromethane, but insoluble in pure water. All the
samples of nano-aggregates of 3a-3c were prepared by the
precipitation method, using THF as soluble solvent and water as
insoluble solvent.
Scheme 1. Molecular structures of 3a-3c.
The corresponding emission spectra of 3a-3c in aqueous THF
with different water/THF ratios at a concentration of 1 × 10-5 M
were shown in Fig. 2. It could be seen that 3a showed weak
fluorescence in pure THF (Fig. 2a). The photoluminescence (PL)
intensity of 3a showed an earlier raised and later decreased state
with increasing the water fraction. It was gradually enhanced
with increasing water/THF ratios below 50 %, which revealed the
increasing aggregate formation. When the water content reached
50 %, the PL intensity boosted to the maximum with an 11-fold
increase in I/I0 ratio (I0 and I represent for the PL intensity before
and after adding water, respectively), therefore 3a exhibits
aggregation-induced emission enhancement (AIEE) activity.
Moreover, the emission maxima of 3a had a red shift of about 20
nm when the water fraction increased from 70 % to 80 %, which
could be ascribed to the increasing accumulation of the
molecules by aggregation leading to a better conjugation.
Similar phenomenon was observed for 3b (Fig. 2b), it
exhibited almost no fluorescence emission when the water
content was below 40 %, while the orange fluorescence reached
the maximum swiftly when water was added up to 50 %, which
is 66 times than that in the pure THF solution, thus 3b exhibited
aggregation-induced emission (AIE) activity. As for 3c (Fig. 2c),
it was non-emissive when the water fraction was below 40 %,
and the yellow fluorescence started to increase gradually at water
content of 50 % and reached the maximum when water was
added up to 90 %, which is nearly 40 times stronger than that in
the pure THF solution, therefore 3c is also AIE active.
Scheme 2. Synthetic route of compounds 3a-3c.
2.2. One-photon absorption properties
Through the measurements by changes of the ΦF with
increasing water content, a quantitative picture of the AIE
process can be made. Even so, the Mie effect of the nano-
aggregate in the mixed solvent could make the ΦF determination
inaccurate.13 So we estimated the integrands of the PL spectra
(see Fig.3a-c) to make comparisons. What’s more, the absorption
The one-photon absorption spectra of 3a-3c in THF solution
are shown in Fig. 1. Compounds 3a-3c revealed onset absorption
wavelength at 564, 510 and 496 nm, respectively. The prominent
red shift in absorption spectrum of 3a was attributed to the
stronger electron-withdrawing ability of A1.

3
spectra of 3a-3c in solution (THF) and in dispersion of the
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nano-aggregate form at 1 × 10-5 M was observed (Fig. 4a-c). It
can be seen that the absorption spectra of 3a-3c in water/THF
mixtures were slightly broadened and red-shifted, which was
caused by nano-aggregation.
However, the PL intensity of 3a was at the maximum value
when the water content was 50 %, a further increase in the water
fraction resulted in a decrease of PL intensity. This phenomenon
is commonly observed in some compounds with AIE properties.
This is probably due to the variation in the packing mode of the
dye molecules in the aggregates. Upon addition of water, the
solute molecules can aggregate into two kinds of nanoparticle
suspensions: crystal particles and amorphous particles. 14
Fig. 4. (a), (b), (c) The absorption spectra of 3a-3c in THF and
THF/water mixtures at a concentration of 1 × 10-5 M; (d) The solid
powder emission spectra of 3a-3c.
Fig. 2. (a), (b), (c) Photoluminescence spectra of 3a-3c, respectively,
in THF/water mixtures.
Fig. 5. (a), (b), (c) SEM images of 3a-3c nano-aggregate prepared in
THF/H2O (10:90 v/v); (d), (e)SEM images of 3a-3b nano-aggregates
prepared in THF/H2O (50:50 v/v) at concentration of 1 × 10-5 M.
Fig. 3. (a), (b), (c) Plots of photoluminescence peak intensity versus
water content of the solvent mixture for 3a-3c; (d), (e), (f) The
emission spectra of 3a-3c in cyclohexane (CHex), toluene (Tol) and
ethanol (EtOH), respectively.
The nanoparticles of 3a-3c were investigated by scanning
electron microscopy (SEM). Fig. 5d-e demonstrate the crystal

4
Tetrahedron
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particles of 3a-3b formed in the solution of THF with 50 %
Table 1 Dihedral angles of the neighboring aromatic rings for 3a-3c.
water, thus 3a-3b actually showed crystallization induced
emission (CIE) effect. In the mixture with lower water fraction,
the dye molecules may assemble in order to form crystalline
aggregates, hence changing 3a-3b to a strong emitter. However,
in the mixture with higher water fraction, the dye molecules
quickly aggregate in a random way and form amorphous particles
(Fig. 5a-b), resulting in the decrease of PL intensity. As for 3c, it
didn’t aggregate into crystal particles which may ascribe to the
suppression caused by its long alkyl chain (Fig. 5c). As the
aggregates increase alone with adding water, the PL intensities
continue to enhance, and boost to the maximum at water ratio of
90 %.
α1
α2
α3
α4
3a
3b
3c
43.4°
44.1°
42.8°
45.2°
44.8°
45.4°
41.5°
40.7°
42.4°
34.8°
34.2°
28.2°
2.6. Two-photon absorption properties
The 2PA cross sections of 3a-3c were determined according
to a previously described method,17 through the femtosecond
open-aperture Z-scan technique (Fig. 7a-c). The 2PA cross
section σ can be calculated by the equation of σ = hνβ/N0, in
which N0 = NAC is the number density of the absorption centres,
NA is the Avogadro constant and C represents the solute molar
concentration. The 2PA σ values for 3a-3c are determined to be
702, 603 and 293 GM, respectively, at the wavelength of 800 nm.
Such AIE properties was also confirmed by the vivid image of
solid powders under 365 nm UV light illumination, as depicted
in Fig. 6. The solid powders were purified by recrystallization
and all the compounds emitted intensely. To quantitatively
evaluate the AIE effect of the fluorescent dyes, the emission
spectra (Fig. 4d) and ΦF of the solid powders were measured.
Compounds 3a-3c reveal emission peaks at 620, 615 and 570 nm,
respectively. The ΦF values are determined to be 8.0 %, 8.1 %,
and 16.4 % for 3a-3c, respectively.
Fig. 6. (a), (b), (c) The images of 3a-3c as solid powders under 365
nm UV light illumination.
2.5. Computational analysis
To better clarify the AIE nature of 3a-3c, the three-
dimensional geometries of the compounds were optimized using
density functional theory (DFT) at the B3LYP/6-31G* level of
theory, using the Gaussian 09 program package.15 In the
calculations, the long alkyl chains were replaced by methyl
groups to save computational time without sacrificing the
reliability of the results. The values of dihedral angles
(α1− α4, shown in Scheme 3) of the neighboring aromatic rings
for 3a-3c are listed in Table 1. It could be conjectured from the
data in Table 1 that all molecules present highly twisted
conformations, which are favorable for intramolecular rotations
in solutions, making them nonemissive in solvents. When
aggregated, not only the intramolecular rotations are hindered,
but also the formation of π-π stacking are prevented, making the
aggregates emit intensely.16 By careful inspection of the data, we
discovered that the corresponding α1− α3 of 3a-3c have almost
Fig. 7. (a), (b), (c) Open-aperture Z-scan trace of 3a-3c (scattered
dots = experimental data, straight line = theoretical fitted data); (d),
(e), (f) At 800 nm excited, the TPF emission spectra of 3a-3c in the
water/THF mixtures at a concentration of 1 × 10-5 M.
no difference, while the α4 of 3c is about 6° smaller compared to
3a-3b, reveals that 3a-3b are more twisted to some extent.
Fig. 8. (a), (b), (c) The TPF emission images of 3a-3c, respectively,
in the water/THF mixtures and pure THF, under illumination with
light of 800 nm; (d), (e), (f)The OPF emission photos of 3a-3c in
the water/THF mixtures and pure THF, under illumination with
light of 365 nm, at a concentration of 1 × 10-5 M.
Scheme 3. The locations of dihedral angles α1−α4 in the molecules.

5
To explain why these dyes displayed 2PA properties, the
3. Conclusion
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result of DFT calculations were reinvestigated. It could be seen
from Fig. S2 that the HOMOs receive contribution from the
multibranched triphenylamine groups, while the LUMOs are
largely localized on the central electrophilic units. Upon
photoexcitation, ICT is expected to occur in these compounds.
The strength of acceptors follow the order of A1 > A2 > A3,
while the planarity of 3a-3c molecules follow the order of 3c >
3b ≈ 3a, owing to the combined factors, 3a showed a largest σ
values of 702 GM. However, the σ values of 3a-3c aren’t
significantly large. We think the introduction of the central
electrophilic unit may have two effects, on one hand, the
conjugation chain was extended; on the other hand, the planarity
of the molecular structure was decreased. Consequently, the
increase of σ value was not remarkable. All results above proved
that the strategies of extending the conjugation chain and
introducing a strong acceptor to the π-bridge can enhance the σ
value of the dye.
In summary, we have developed three 2PA dyes 3a-3c with
AIE property. They are almost non-emissive in pure THF, but
with the increasing water content in THF solution, they exhibit
notable enhanced deep yellow, orange and yellow fluorescence,
respectively. In addition, the solid state of 3a-3c also reveals
quite strong fluorescence emission with the corresponding ΦF
value of 8.0 %, 8.1 % and 16.4 %, respectively. All molecules
exhibit the feature of aggregation-enhanced two-photon excited
fluorescence, their 2PA σ values are 702, 603, and 293 GM,
respectively, at wavelength of 800 nm. The result demonstrates
that the strategies of extending the conjugation chain and
employing a stronger acceptor can enhance the 2PA σ value of
the dye. This work could provide a guideline for the design of π-
conjugated organic dyes with enhanced 2PA properties.
Table 2 Electrochemical and optical properties of 3a-3ca
Eonset-ox (V) HOMO (eV) λonset (nm) Eg (eV) LUMO (eV)
Compounds 3a-3c in a mixture of water and THF exhibit
intense TPF emission centered at 611, 615 and 604 nm (Fig. 7d-
f), under the excitation of 80 fs, 800 nm pulse. Compared with
the spectra in Fig. 2, the good overlap between one-and two-
photon excitation fluorescence indicates that the emissions
resulted from the same excited state, regardless of the different
mode of excitation. Fig. 8 shows the one- and two-photon
emission images in pure THF and water/THF mixtures. Under
illumination with light of 800 and 365 nm, owing to their nano-
aggregates suspending in water/THF mixtures, dyes 3a-3c exhibit
different fluorescent colors: deep yellow, orange and yellow,
respectively, while almost no emission is observed in pure THF.
As for the limitation of our laser apparatus, only irradiation at
one wavelength of 800 nm was used to carry out the two-photon
excitation experiment.
3a
3b
3c
0.88
0.90
0.91
- 5.58
- 5.60
- 5.61
564
510
496
2.20
2.43
2.50
- 3.38
- 3.17
- 3.11
a
Abbreviation: Eonset-ox = onset oxidation potential measured by cyclic
voltammetry, HOMO= - (Eonset-ox + 4.7) eV, λonset = onset absorption
wavelength, Eg = energy band gap determined form λonset, LUMO = Eg
+
HOMO.
4. Experimental Section
4.1. Materials
THF was pre-dried over sodium for 24 h and then redistilled
under argon atmosphere with sodium prior to use. DMF was
refluxed with calcium hydride and distilled before use. All other
chemicals were purchased from commercial sources (J&K,
Aldrich) and used as received without further purification.
4.2. Instruments
1H and 13C NMR spectra were measured on a Bruker AM-400
spectrometer using d-chloroform as solvent and tetramethylsilane
(TMS, δ = 0 ppm) as internal standard. Mass spectra were
recorded on an AB Sciex 4800 plus Matrix-Assisted Laser
Desorption Ionization Time of Flight (MALDI-TOF) mass
spectrometer. The UV/Vis spectra were recorded on a Nicolet
CARY 100 spectrophotometer. The PL spectra were taken on a
Varian-Cary fluorescence spectrophotometer. The quantum yield
for solid powders was measured by Quanta-w F-3029 Integrating
Sphere. The melting point was measured on a Hanon MP100
automatic melting point apparatus. The 2PA cross sections were
measured by a femtosecond open aperture Z-scan technique
according to a previously described method. The TPF was
achieved using femtosecond pulses with different intensities at a
wavelength of 800 nm. The repetition rate of the laser pulses was
250 KHz and the pulse duration was 80 fs. The cyclic
voltammograms of 3a–3c were obtained using a Versastat II
electrochemical workstation.
Fig. 9. Cyclic voltammograms of 3a-3c in THF with 0.1 M of
tetrabut-ylmmonium hexafluorophosphate (n-Bu4NPF6).
2.7. Electrochemical properties
The electrochemical properties of 3a-3c were investigated by
cyclic voltammetry (CV). The energy level parameters of the 3a-
3c are listed in Table 2. The cyclic voltammetry of 3a-3c was
measured in CH2Cl2 (0.1
M n-Bu4NPF6 as supporting
electrolyte), with an SCE reference electrode, platinum-button
working electrodes, and a platinum-wire counter electrode, as
shown in Fig. 9. Onset oxidation potentials of 3a–3c can be
calculated from the figure to be 0.88, 0.90, and 0.91V,
respectively. Thus, the HOMO values for 3a-3c are -5.58, -5.60, -
5.61 eV, respectively, derived from onset oxidation potentials
given above. The band gaps of 3a-3c can be determined from
their onset absorption wavelengths and are calculated to be 2.20,
2.43, and 2.50 eV, respectively.
4.3. Synthesis
3,6-bis(4-bromophenyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione
(1a): Sodium (4.6 g, 0.2 mol) was cut into pieces and slowly
added to 100 mL anhydrous tert-amyl alcohol in a two-neck flask.
After stirring for 3 h, 4-bromobenzonitrile (18.2 g, 0.1 mol) was
added to the flask and 8 mL diisopropyl succinate dissolved in 30
mL anhydrous tert-amyl alcohol was dropwise added to the
reaction mixture under N2 atmosphere. Then the mixture was

6
Tetrahedron
o
stirred for 12 h at 90 C, upon cooling the mixture was washed
chromatography on silica (petroleum ether/CH2Cl2 = 4 : 1 v/v) to
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1
with acetic acid and water. After vacuum drying, 11.5 g red solid
was obtained. Yield: 71.6 %. The product was used without
further purification.
give a yellow solid (2.45 g). Yield: 73 %. H NMR (DMSO-d6,
400 MHz, TMS), δ: 7.53 (d, J = 8.5 Hz, 2H), 7.36 (dt, J = 15.2,
7.8 Hz, 10H), 7.21 (m,10H), 7.03 (d, J = 7.8 Hz, 4H), 6.92 (d, J =
8.8 Hz, 2H), 6.87 (d, J = 8.5 Hz, 2H), 6.75 (d, J = 8.6 Hz, 2H).
3,6-bis(4-bromophenyl)-2,5-dibutylpyrrolo[3,4-c]pyrrole-1,4(2H,
5H)-dione (2a): In a two-neck flask, 2a (4.46 g, 10 mmol) and
potassium tert-butoxide (3.36 g, 30 mmol) were dissolved in 120
mL DMF and stirred for 2 h at r.t., then butyl iodide (5.52 g, 30
mmol) was dropwise added to the mixture, and stirred for 6 h at
3,3-Bis(4-(diphenylamino)phenyl)-2-(4-(4,4,5,5-tetramethyl-1,3,
2-dioxaborolan-2-yl)phenyl)acr-ylonitrile (I3): Compound I2 (2
g, 2.88 mmol), bis(pinacolato)diboron (1.1 g, 4.32 mmol), KAc
(0.85 g, 8.64 mmol) and Pd(dppf)Cl2 (10 mg) were dissolved into
50 mL anhydrous dioxane, under N2 atmosphere the mixture
o
90 C. Upon cooling, DMF was removed by reduced pressure
o
distillation, the residue was poured into 100 mL water and
extracted with CH2Cl2 (50 mL × 3), the combined organic layer
was washed with water and then concentrated using a rotary
evaporator. The residue was purified by column chromatography
on silica (petroleum ether/CH2Cl2 = 2 : 1 v/v) to give a red solid
(1.95 g). Yield: 35 %. H NMR (CDCl3, 400 MHz, TMS), δ:
7.65-7.71 (m, 8H), 3.74 (t, J = 7.2 Hz, 4H), 1.54 (t, J = 7.2 Hz,
2H), 1.21-1.31 (m, 6H), 0.85 (t, J = 7.2 Hz, 6H).
were heated to 100 C, then stirred for 10 h, upon cooling, the
mixture was poured into water and extracted with CH2Cl2 (20 mL
× 3), the combined organic layer was washed with water and was
dried over anhydrous MgSO4 and then concentrated using a
rotary evaporator. The residue was purified by column
chromatography on silica (petroleum ether/CH2Cl2 = 3 : 1 v/v) to
1
1
give a yellow solid (1.4 g). Yield: 65 %. H NMR (CDCl3, 400
MHz, TMS), δ: 7.66 (d, J = 8.2 Hz, 2H), 7.29 (m, 12H), 7.17 (d,
J = 7.5 Hz, 4H), 7.06 (dt, J = 17.0, 8.3 Hz, 10H), 6.81 (dd, J =
20.8, 8.8 Hz, 4H), 1.35 (s, 12H).
2-octyl-2H-benzo[d][1,2,3]triazole (1c): In a two-neck flask, 2H-
benzotriazole (1 g, 8.4 mmol) and sodium hydroxide (0.4 g, 10
mmol) were dissolved in 20 mL DMSO, and catalytic amount of
tetrabutylammonium bromide was added, then 1-bromooctane
(1.9 g, 10 mmol) was dropwise added under N2 atmosphere. The
mixture was stirred for 12 h at r.t. and poured into 100 mL water,
extracted with CH2Cl2 (50 mL × 3), the combined organic layer
was washed with water and concentrated using a rotary
evaporator. The residue was purified by column chromatography
on silica (petroleum ether/CH2Cl2 = 4 : 1 v/v) to give a white
solid (1.4 g). Yield: 72 %. 1H NMR (CDCl3, 400 MHz, TMS), δ:
7.87 (m, 2H), 7.37 (m, 2H), 4.72 (t, J = 7.6 Hz, 2H), 2.12 (m,
2H), 1.34-1.22 (m, 10H), 0.86 (t, J = 7.2 Hz, 3H).
2,2'-((2,5-dibutyl-3,6-dioxo-2,3,5,6-tetrahydropyrrolo[3,4-c]pyrr-
ole-1,4-diyl)bis([1,1'-biphenyl]-4',4-diyl))bis(3,3-bis(4-(dipheny-
lamino)phenyl)acrylonitrile) (3a): Compound I3 (0.23 g, 0.31
mmol), compound 2a (0.08 g, 0.14 mmol) were dissolved in 20
mL THF, then was put 5 mL saturated sodium bicarbonate
solution and 5 mg Pd(dppf)Cl2, under N2 atmosphere the mixture
o
were heated to 80 C, then stirred for 10 h. Upon cooling, the
mixture was poured into water and extracted with CH2Cl2 (10 mL
× 3), the combined red layer was washed with water and was
dried over anhydrous MgSO4, then concentrated using a rotary
evaporator. The residue was purified by column chromatography
on silica (petroleum ether/CH2Cl2 = 2 : 1 v/v) to give an red solid
(0.1 g). Yield: 44 %; m.p.: ＞ 300 oC. FTIR (KBr, cm-1): 3060.63,
3033.63 (υ, ＝C－H), 2956.48, 2871.63 (υ, CH3), 2929.49 (υ,
CH2), 2200.49 (υ, C≡N), 1679.22 (υ, R－N－C＝O), 1589.45,
1491.76 (υ, Ar－C＝C), 1328.37 (Ar－C－N). 1H NMR (CDCl3,
400 MHz, TMS), δ: 7.94 (d, J = 8.4 Hz, 4H), 7.76 (d, J = 8.4 Hz,
4H), 7.55 (d, J = 8.4 Hz, 4H), 7.40 (dd, J = 16.8, 8.4 Hz, 8H),
7.31 (m, 11H), 7.24-7.26 (m, 7H), 7.18 (d, J = 7.6 Hz, 8H), 7.02-
7.11 (m, 21H), 6.92 (d, J = 8.8 Hz, 4H), 6.84 (d, J = 8.8 Hz, 4H),
3.83 (t, J = 7.2 Hz, 4H), 1.65 (m, 5H), 1.32 (m, 6H). 13C NMR
(CDCl3, 100 MHz), δ: 162.82, 157.69, 149.54, 148.71, 147.98,
146.93, 146.86, 142.85, 138.99, 135.92, 132.71, 132.38, 131.65,
131.52, 130.31, 129.49, 129.43, 129.27, 127.32, 126.94, 125.61,
125.36, 124.02, 123.91, 121.17, 120.80, 120.59, 110.02, 106.99,
41.90, 29.70, 20.05, 13.66. MALDI-TOF (m/z): M calcd for:
C116H90N8O2, 1626.7187, found: 1626.7218.
4,7-dibromo-2-octyl-2H-benzo[d][1,2,3]triazole (2c): In a two-
neck flask, compound 1c (1 g, 4.3 mmol) was dissolved in 70 mL
HBr (ω ≈ 40 %), bromine (2 g, 12.5 mmol) in 50 mL HBr was
slowly added to the flask, the mixture was stirred and refluxed
for 6 h. Upon cooling, a white solid precipitate was filtered off
and washed with water. The residue was purified by column
chromatography on silica (petroleum ether/CH2Cl2 = 4 : 1 v/v) to
give a white solid (1.1 g). Yield: 66 %. H NMR (CDCl3, 400
MHz, TMS), δ: 7.45 (s, 2H), 4.78 (t, J = 7.6 Hz, 2H), 2.15 (m,
2H), 1.26-1.38 (m, 10H), 0.87 (t, J = 7.2 Hz, 3H).
1
Bis(4-(diphenylamino)phenyl)methanone (I1): In a two-neck
flask, diphenylamine (6.2 g, 36.7 mmol) and sodium tert-
butoxide (5.28 g, 55 mmol) were dissolved in 100 mL anhydrous
DMF, and 4 g bis(4-fluorophenyl)-methanone (18.3 mmol)
dissolved in 50 mL anhydrous DMF was dropwise added into the
flask under N2 atmosphere. The reaction mixture was refluxed for
10 h. Upon cooling the mixture was poured into 200 mL ice
water, a deep yellow solid precipitate was filtered off and washed
with ethanol. After vacuum drying, a 7.85 g yellow solid was
2,2'-(benzo[c][1,2,5]thiadiazole-4,7-diylbis(4,1-phenylene))bis-
(3,3-bis(4-(diphenylamino)phenyl)acrylonitrile) (3b): Compound
3b was synthesized by the same procedure as described above for
3a using compound 2b and compound I3. Yield: 55 %; m.p.: ＞
1
obtained. Yield: 83 %. H NMR (CDCl3, 400 MHz, TMS), δ:
7.74 (m, 4H), 7.35 (m, 8H), 7.22 (m, 8H), 7.14 (m, 4H), 7.02 (d,
o
300 C. FTIR (KBr, cm-1): 3058.70, 3033.63 (υ, ＝ C － H),
2198.56 (υ, C≡N), 1588.67, 1490.18 (υ, Ar－C＝C), 1329.79 (Ar
－C－N). 1H NMR (CDCl3, 400 MHz, TMS), δ: 7.91 (d, J = 8.4
Hz, 4H), 7.80 (s, 2H), 7.49 (d, J = 8.8 Hz, 4H), 7.39 (d, J = 8.8
Hz, 4H), 7.31 (t, J = 8 Hz, 9H), 7.21 (m, 15H), 7.10 (t, J = 8.8
Hz, 12H), 7.01-7.06 (m, 8H), 6.97 (d, J = 8.8 Hz, 4H), 6.86 (d, J
= 8.8 Hz, 4H). 13C NMR (CDCl3, 100 MHz), δ: 157.72, 154.01,
149.56, 148.70, 146.96, 146.91, 136.49, 136.09, 132.78, 132.60,
132.43, 131.85, 131.56, 129.95, 129.51, 129.42, 129.12, 128.02,
125.62, 125.32, 124.03, 123.85, 121.19, 120.98, 120.64, 107.22.
MALDI-TOF (m/z): M calcd for: C96H66N8S, 1362.5131, found:
1362.5164.
J = 8.8 Hz, 4H).
2-(4-Bromophenyl)-3,3-bis(4-(diphenylamino)phenyl)acrylonitr-
ile (I2): Compound I1 (3 g, 5.8 mmol), 60 % NaH (0.92 g, 23.2
mmol) were put into a two-neck flask and dissolved into 50 mL
dry toluene, and 2-(4-bromophenyl)acetonitrile (1.13 g, 5.8
mmol) in 50mL dry toluene solution was dropwise added into the
flask under N2 atmosphere. The mixture was stirred and refluxed
for 8 h, then poured into water upon cooling and extracted with
CH2Cl2 (50 mL × 3), the combined organic layer was washed
with water and was dried over anhydrous MgSO4, concentrated
using a rotary evaporator. The residue was purified by column

7
11. (a) Rumi, M., Ehrlich, J. E., Heikal, A. A., Perry, J. W., Barlow, S.,
2,2'-((2-octyl-2H-benzo[d][1,2,3]triazole-4,7-diyl)bis(4,1-phenyl-
ACCEPTED MANUSCRIPT
Hu, Z., McCord-Maughon, D., Paker, T. C., Thayumanavan, S.,
Marder, S. R., Beljonne D. J. Am. Chem. Soc., 2000, 122, 9500-9510;
(b) Zheng, S. J., Beverina, L., Barlow, S., Zojer, E., Fu, J., Padilha,
L.A., Fink, C., Kwon, O., Yi, Y. P., Shuai, Z. G., Stryland, E. W.V.,
Hagan, D. J., Marder, S. R. Chem. Commun., 2007, 1372-1374.
12. Yang, Z. Y.; Chi, Z. G.; Xu, B. J.; Li, H. Y.; Zhang, X.Q.; Li, X. F.; Liu,
S. W.; Zhang Y.; Xu, J. R. J. Mater. Chem. 2010, 20, 7352-7359.
13. Liu, Y.; Tao, X. T.; Wang, F.; Shi, J.; Sun, J.; Yu, W.; Ren, Y.; Zou, D.;
Jiang, M. H. J. Phys. Chem. C 2007, 111, 6544.
ene))bis(3,3-bis(4-(diphenylamino)phenyl)acrylo-nitrile)
(3c):
Compound 3c was synthesized by the same procedure as
described above for 3a using compound 2c and compound I3.
o
Yield: 38 %; m.p.: ＞ 300 C. FTIR (KBr, cm-1): 3059.08,
3034.12 (υ, ＝C－H), 2951.58 (υ, CH3), 2922.95, 2853.74 (υ,
CH2), 2200.48 (υ, C≡N), 1589.64, 1490.96 (υ, Ar－C＝C),
1
1330.45 (Ar－C－N). H NMR (CDCl3, 400 MHz, TMS), δ:
8.01 (d, J = 8.4 Hz, 4H), 7.66 (s, 2H), 7.46 (d, J = 8.4 Hz, 4H),
7.38 (d, J = 8.8 Hz, 4H), 7.31 (t, J = 8 Hz, 8H), 7.21 (m, 16H),
7.10 (t, J = 8 Hz, 12H), 7.01-7.05 (m, 8H), 6.96 (d, J = 8.8 Hz,
4H), 6.85 (d, J = 8.4 Hz, 4H), 2.12-2.20 (m, 2H), 1.25-1.39 (m,
12H), 0.83-0.87 (m, 3H). 13C NMR (CDCl3, 100 MHz), δ:
157.35, 149.48, 148.62, 146.99, 146.92, 143.41, 136.47, 135.54,
132.90, 132.39, 132.01, 131.53, 130.00, 129.50, 129.40, 128.35,
125.59, 125.27, 124.41, 123.99, 123.81, 121.21, 121.03, 120.69,
107.52, 56.90, 30.96, 30.22, 29.13, 29.01, 26.65, 22.62, 14.11.
MALDI-TOF (m/z): M calcd for: C104H83N9, 1457.6771, found:
1457.6879.
14. (a) Kim, S.; Zheng, Q. D.; He, G. S.; Bharali, D. J.; Pudavar, H. E.;
Baev, A.; Prasad, P. N. Adv. Funct. Mater. 2006, 16, 2317-2323; (b)
Dong, Y. Q.; Lam, J. W. Y.; Qin, A. J.; Sun, J. X.; Liu, J. Z.; Lin, Z.;
Sun, Z. Z.; Sung, H. H. Y.; Williams, I. D.; Kwok, H. S.; Tang, B. Z.
Chem. Commun. 2007, 3255-3257; (c) Zhang, Z. Y.; Xu, B.; Su, J. H.;
Shen, L. P.; Xie, Y. S.; Tian, H. Angew. Chem., Int. Ed. 2011, 50,
11654-11657.
15. (a) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb,
M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.;
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Acknowledgements
This work was supported by NSFC/China (20772031), the
National Basic Research 973 Program (2006CB806200), the
Fundamental Research Funds for the Central Universities
(WJ0913001), and the Scientific Committee of Shanghai
(10520709700).
16. Yuan, W. Z.; Gong, Y. Y.; Chen, S. M.; Shen, X. Y.; Lam, J. W. Y.; Lu,
P.; Lu, Y. W.; Wang, Z. M.; Hu, R. R.; Xie, N.; Kwok, H. S.; Zhang, Y.
M.; Sun, J. Z.; Tang, B. Z. Chem. Mater. 2012, 24, 1518−1528.
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Supplementary data
The computational analysis data and characterization (NMR
and MS
) of 3a-3c are available.
References and notes
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Electronic Supplementary Information (ESI)
New cyano-substituted organic molecules containing different
electrophilic groups: aggregation-induced emission and large
two-photon absorption cross sections
Haitao Zhou, Wei Huang, Li Ding, Xin Li, Bo Li and Jianhua Su*
Key Laboratory for Advanced Materials and Institute of Fine Chemicals, East China
University of Science & Technology, Shanghai 200237, China
E-mail: bbsjh@ecust.edu.cn
fax: +86 21-64252288
1. Fig. S1 The optimized geometries of 3a-3c.
2. Fig. S2 Frontier molecular orbital contours of 3a-3c.
3. Fig. S3 The 1H NMR spectra of 3a-3c.
4. Fig. S4 The 13C NMR spectra of 3a-3c.
5. Fig. S5 The mass spectra of 3a-3c.
6. Fig. S6 The pictures of 3a-3c in THF/H2O mixture taken after adding water for
several hours.
7. Fig. S7 The IR spectra of 3a-3c.

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Compound
Topview
Sideview
3a
3b
3c
Fig. S1 The optimized geometries of 3a-3c.
Compound
HOMO
LUMO
3a
3b
3c
Fig. S2 Frontier molecular orbital contours of 3a-3c.

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Fig. S3 (a),(b),(c) The 1H NMR spectra of 3a-3c, respectively.

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Fig. S4 (a),(b),(c) The 13C NMR spectra of 3a-3c, respectively.

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Fig. S5 (a),(b),(c) The mass spectra of 3a-3c, respectively.

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Fig. S6 (a),(b),(c) The pictures of 3a-3c, respectively, in THF/H2O mixture taken after
adding water for several hours.

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Fig. S7 (a),(b),(c) The IR spectra of 3a-3c, respectively.