Synthesis and characterizations of novel spindle-like terphenyl-type chromophores for non-linear optical materials

Article abstract of DOI:10.1016/j.tet.2011.03.108

A series of novel spindle-like terphenyl-type chromophores, based on 2,5-diphenyl-1,4-distyrylbenzene π-conjugating bridge, N,N-dimethyl and triphenyl amino donors, and Tricyanovinyldihydrofuran(TCF), 1,3,3-trimethyl-5- dicyanovinyl-1-cyclohexene (TDC) acceptors, have been synthesized successfully for the first time. And the non-linear optical properties were evaluated by using the finite-field (FF) method. The results show that, the first-order hyperpolarizability of the chromophores increase with the increase of the withdraw ability of the substituent group on the π-conjugating bridge.

Full text of DOI:10.1016/j.tet.2011.03.108

Tetrahedron 67 (2011) 4110e4117
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Synthesis and characterizations of novel spindle-like terphenyl-type
chromophores for non-linear optical materials
,
Zuosen Shi a, Xiaolong Zhang a, Guochun Yang b, Zhongmin Su b, Zhanchen Cui a
*
a State Key Lab for Supramolecular Structure and Materials, College of Chemistry, Jilin University, 2699# Qianjin Road, Changchun 130012, PR China
b Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
A series of novel spindle-like terphenyl-type chromophores, based on 2,5-diphenyl-1,4-distyrylbenzene
Received 29 November 2010
Received in revised form 23 March 2011
Accepted 30 March 2011
p
-conjugating bridge, N,N-dimethyl and triphenyl amino donors, and Tricyanovinyldihydrofuran(TCF),
1,3,3-trimethyl-5-dicyanovinyl-1-cyclohexene (TDC) acceptors, have been synthesized successfully for
the first time. And the non-linear optical properties were evaluated by using the finite-field (FF) method.
The results show that, the first-order hyperpolarizability of the chromophores increase with the increase
Available online 7 April 2011
of the withdraw ability of the substituent group on the
p
-conjugating bridge.
Ó 2011 Elsevier Ltd. All rights reserved.
Keywords:
NLO
Chromophore
Optical
Terphenyl
1. Introduction
organic light-emitting diodes (OLED) and lasers.9 In our view, these
types of molecules have never been used in non-linear optical
materials, and their unique structure could effectively prevent the
aggregation of the chromophores in the poled films and greatly
improve the temporal and long term stability.10
In pursuit of chromophores with large optical nonlinearity,
thermal stability, and high optical transparency, many rules and
principles have been proposed by Dewar, Dalton, Alex, etc.11 By
following Dalton’s principles, the shape of the chromophores may
play an important role in determining NLO response of the mate-
rial, and spherical chromophores may be the ideal shape for NLO
materials. Through this designation, Dalton found the spectra
shift1c of intramolecule charge-transfer transition of chromophore
when changing the molecule shapes.
Therefore, to achieve the major challenging topic of the
nonlinearity-transparency trade-off, in this paper, we synthesized
a series of novel chromophores (Chart 1) with terphenyl moiety as
the conjugating bridge, tripenylamino and alkyl amino as the donor
groups, Tricyanovinyldihydrofuran(TCF), 1,3,3-trimethyl-5-dicya-
novinyl-1-cyclohexene (TDC) as accepters by a Suzuki coupling
reaction and Wittig reaction, their structures were fully character-
ized by NMR, FTIR, elemental analysis, and differential scanning
calorimeter (DSC) methods. Moreover, we explored the structur-
eeproperty relationship by changing the substituent groups on the
During the past decade, organic molecules for non-linear optical
materials were deeply researched, because of their potential ap-
plications in ultrafast electro-optic modulations.1e3 A lot of mole-
cules with large hyperpolarizabilities and excellent thermal and
chemical stabilities were synthesized.4e6
Most of those types of chromophores have the traditional one
dimension Dep-A structures, the design and synthesis of
donoreacceptor substituted hetero aromatic compounds have
attracted widespread interest because it was experimentally and
theoretically demonstrated that these structures could effectively
improve the second-order non-linear optical (NLO) properties of
the chromophores. The mb values of these chromophores developed
by Alex etc.1c,3a are even larger than 18 000ꢀ10ꢁ48 esu. At the same
time, tetrapolar and octupolar1dꢁh molecules were researched
widely, some interesting molecules, such as L, X, Y, and H, etc.
types7,8 were also developed and indicated good second-order
linear optical properties. For the practical application of second-
order NLO materials, the chromophores need to have a large
hyperpolarizability, good thermal stability and low optical loss. In
the recent years, terphenyl compounds have been deeply studied
because of their excellent electro-optic properties in application of
p-conjugating bridge from electron-donating group to electron-
drawing group, which shows that the stronger of the electron-
drawing ability, the larger of the first-order hyperpolarizability.
* Corresponding author. Tel.: þ86 431 85168217; fax: þ86 431 85193423; e-mail
address: cuizc@jlu.edu.cn (Z. Cui).
0040-4020/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2011.03.108

Z. Shi et al. / Tetrahedron 67 (2011) 4110e4117
4111
electron-donating group, an upfield shift of Ha will be obtained.13,14
From the Fig.1 we can see that all of the aromatic substituted groups
act as electro-drawing groups to make downfield chemical shift of
Ha. Compared with compound 8a, the chemical shift of Ha in com-
pound 8b and 8c located at 8.06 ppm and 8.12 ppm, respectively. The
chemical shift of Ha in compound 8d is at 8.16 ppm suggesting that
the thiophene group acts as a strong electron-withdrawing group.
Compared to the unsubstituted compound 1(reported by Qin12c),
the electronic effect of aromatic groups at the conjugating bridge
play great role, two aromatic Hb and Hc neighboring the aromatic
substitutes in all chromophores experience significant deshielding
of chemical shifts compared to the corresponding protons in com-
pound 1 (7.45e7.48 ppm), which implies that the aromatic groups
result in decreased electron density at the phenyl ring and cause the
attached protons resonate at a lower field. While from 1H NMR data,
which are listed in Table 1, both of the chemical shift of Hb and Hc
indicated the same trends. The 4-trifluoromethylphenyl and thienyl
substituted chromophores exhibit electron-drawing effect to make
the chemical shift move to a lower field, while 4-methoxyphenyl
substituted chromophore exhibit electron-donating effect to make
the chemical shift move to a higher field.
The UVevis absorption spectra are employed to explore the
differing
p-conjugating bridge properties of the modified conju-
gating bridges. The UVevis absorption spectra of compounds 1, 2a,
2b, 4, and 5 in dichloromethane are displayed in Fig. 2(a) and all of
the photophysical data are listed in Table 2.
Compared to chromophore 1, these spectra show multiple ab-
sorption peaks, and the lower-lying peaks are relatively strong. This
relatively strong low-lying absorption in these chromophores
Chart 1. Structures of the chromophores.
maybe due to the
p
e
p
*
transition of the aromatic ring substituted
-conjugating bridge
2. Results and discussion
in the -conjugating bridge. Replacing the
p
p
with the substituted phenyl group, has a profound effect on the
charge-transfer bands resulting in 64 nm, and 43 nm, respectively,
blue-shifted values for chromophores 2c and 2b (Fig. 2a). And it
2.1. Synthesis and characterization
Scheme 1 shows the synthesis of the two electro-donor groups,
N,N-dimethyl-phenylamino-triphenylphosphorus methyl bromide
was directly synthesized according to Raimundo’s report12a and
synthesis of Triphenyl amino(TPA)-triphenylphosphorus methyl
bromide(6) need three steps, first, single-aldehyde was prepared
via Vilsmeier formylation in the presence of POCl3 and N,N-di-
methyl formylation(DMF); then it was reduced by sodium boron
tetrahydride; Compound 6 was finally obtained by further reaction
with triphenyl phosphorus bromide in high yields.
2,5-dibromo-1,4-dialdehyde-benzene (7) was prepared by the
method similar with its isomer 1,2-dibromo-4,5-dialdehyde-ben-
zene, which has been reported before.9,12d
The key intermediates terphenyl-1,4-dialdehydes compounds
(8aec) and 2,5-dithienyl-1,4-dialdehyde-benzene(8d) were readily
prepared by a Pd(0)-catalyzed Suzuki cross-coupling reaction of 4-
methoxyphenylboronic acid, 4-phenylboronic acid, 4-(tri-
fluoromethyl) phenylboronic acid and thiophene-2-boronic acid
with Compound 7.
means that groups substituted in the
p-conjugating bridge can
greatly affect the transition states of these chromophores, and this
variation maybe potentially influence their NLO properties.15
It should be noted that the lmax of the compound 2aec are all
red-shifted (35e62 nm), while compound 3aec, 4 and 5 are blue
shifted (7e26 nm) upon increasing the solvent dielectric constant
from CH2Cl2 to DMF (see Table 2). An extended solvatochromic
study was attempted for Compound 5; the spectra are overlain in
Fig. 2b. While the charge-transfer band showed decent sol-
vatochromic red-shift upon increasing the solvent dielectric con-
stant, there appears to be a threshold for this behavior for
compound 5 that there occurs a reversal of the lmax upon in-
creasing the dielectric constant to beyond 9.8 [CH2Cl2 and DMF
(37.6) appear to favor excessive charge transfer in this compound]
leading to back electron donation causing blue-shift from the ab-
sorption in chloroform. This confirms the concept that chromo-
phores 5 are more strongly polarizable than 2aec.14 The optimized
structures of some of the chromophores are shown in Fig. 3.
Synthesis of NLO chromophores containing diphenylphenyl and
dithinylphenyl as the conjugating bridges is shown in Scheme 1.
The compound 6 and two different acceptors, 1,3,3-trimethyl-5-
dicyanovinyl-1-cyclohexene(TDC) and Tricyanovinyldihydrofuran
(TCF) were used for the chromophore synthesis by the Knoevenagel
condensation reactions.
To clarify the influence of the group substituted on the conju-
gating bridge, a series of aromatic groups, with electro-donor group
or electro-acceptor group, were synthesized to systematically
compare their electronic effect. Fig. 1 shows the 1H NMR spectra of
compound 8aed, and terephthalaldehyde served as a reference
value. The reference value is located at 8.05 ppm, and any electron-
withdrawing group introduced neighboring Ha, resulting in
a downfield shift of Ha relative to 8.05 ppm. If the substitute is an
2.2. Thermal stability
Thermal properties of these chromophores were explored by
differential scanning calorimetry and are shown in Fig. 4. All of the
compounds have a range of melting point (mp) of 200e300 ꢂC,
except chromophore 4 at about 165 ꢂC. As shown in Table 2, all
chromophores exhibit good thermal stability with onset de-
composition temperatures over 200 ꢂC. Substitutes on the ter-
phenyl groups cause a significant decrease of decomposition
temperatures (Td). An acceptor dependence of thermal stability
was observed for the resulting NLO chromophores. 2aec, 4, and 5
containing TDC group as electro-acceptor exhibited the highest

4112
Z. Shi et al. / Tetrahedron 67 (2011) 4110e4117
Scheme 1. Synthetic route of the terphenyl-type chromophores.
stability at up to 386 ꢂC compared to corresponding chromophores
with TCF as electro-acceptor (Fig. 5).
on the SHG signal and a solution-based hyper-Rayleigh scattering
).7a,14,16ꢁ18 The-
measurements for the important term bHRS(ꢁ2
u;u,u
oretical calculation can help to rationalize the experimental results
and rank the existing molecular structures according to their linear
and non-linear susceptibilities prior to experiment and thus to pro-
pose new promising compounds to chemists.19 In the past decade,
advances in computer technology and methodology of molecular
orbital calculation make it possible to calculate response properties
2.3. Non-linear optical properties
The static hyperpolarizability reflect the intrinsic polarization of
the moleculesatzerofrequency, generallythereareseveralmethodto
measure the
b values of chromophores, such as EFISH method based

Z. Shi et al. / Tetrahedron 67 (2011) 4110e4117
4113
Properly selective method and basis set are the premise of ac-
curate predication NLO response. The structures of our studied
compounds are similar to that of para-nitroaniline (PNA). First PNA
was taken as an example to test the reliability of our adopted
method. The first-order hyperpolarizablity values of PNA using the
B3LYP/6-31G
*
and B3LYP/6-311þþG** are 6.62 and 7.99, re-
spectively, which are very close to the experimental value (9.2).20a
To save the computational time, the B3LYP/6-31G
following calculation.
*
was used in the
The first-order hyperpolarizablity of all compounds were calcu-
lated by the FFand method at the B3LYP/6-31G level. Due tothe lack
*
of experimental value, three kind of first-order hyperpolarizabilities
value are calculated and given in Table 3. The results show that the
b
values of 2aec decreased in comparisonwith reference compound
1 when the -conjugating bridgechanged fromphenyltoterphenyl-
p
type groups. It may be caused by the bad delocalization of the
intramolecular charge transparency, which was demonstrated by
the UV study. Moreover, the first-order hyperpolarizabilities of these
compounds (2aec, 3aec) are related to the substituted group on the
Fig. 1. 1H NMR spectra of the compound 8aed.
phenyl group of
p-conjugating bridge. A substitution with an
electro-drawing group CF3 (2c) improves the NLO property, an
electro-donating group OCH3 (2b) displays a little decrease refer-
enced with nonsubstituted compound 2a. Compounds with TCF as
Table 1
Chemical shift of the Hb and Hc in chromophores 2aec and 5
1
2a
2b
2c
4
5
the electro-acceptor group display larger
b values than chromo-
Hb
Hc
7.45
7.45
7.68
7.73
7.68
7.69
7.77
7.79
7.66
7.69
7.72
7.91
phores with TDC as the electro-acceptor. Introduction of TPA group
Fig. 2. (a) UVevis spectra of the chromophores in CH2Cl2; (b) UVevis spectra of chromophore 5 in different solvents varying dielectric constants (dioxane: 2.25; toluene: 2.38;
CHCl3: 4.81; CH2Cl2: 9.8; DMF: 37.6).
due to higher-order perturbation in molecular systems within a re-
alistic computation time.20 Moreover, the prediction values of new
chromophores based on theoretical calculation, and often give very
close results to experimental values.18 Thus density functional theory
(DFT) quantum mechanical methods were employed to determine
in compound 4 and 5 enhanced second-order NLO properties. Fi-
nally we can conclude that the matching of suitable electro-donor
and acceptor and a suitable electro-drawing substituted group on
the
p
-conjugating bridge could play a great role in designing NLO
values.
chromophores with large
b
theoretical
b (0; 0,0) values for the chromophores.
Table 2
2.4. Orientation stabilities of chromophores in poled films
Summary of optical absorption data
Compd
lmax(nm)
CH2Cl2
lmax(nm)
DMF
3
(104Mꢁ1cmꢁ1
)
D
E(UV)a(eV)
Tdb(ꢂC)
Fig. 6 shows the UVevis absorption spectrum of the poled films,
from which we observe a decrease in absorption after poling. Fur-
thermore, according to the absorbance change, we also estimated
1
482
425
439
417.5
473.5
482
498
453
486
460
481
479
4.8
1.6
3.03
6.9
1.2
1.6
2.1
4.2
3.33
2.10
2.28
2.29
2.49
2.09
2.09
2.05
2.23
2.20
250
375
350
300
297
290
290
386
350
2a
2b
2c
3a
3b
3c
4
the order parameter (
F
¼1ꢁAp/A0) of the two kinds of poled films
(0.19 and 0.38, respectively, for polymers 1/PMMA and 2a/PMMA),
which is related to the poling efficiency.21 The result indicated that
2a/PMMA was poled more effectively than 1/PMMA in the same
poling conditions, and it maybe due to the unique shape of the
chromophores, which could decrease the intermolecular dipo-
leedipole interactions and chromophore aggregation.
447
470.5
474.5
446
5
464
457
a
Estimated from the onset of the absorption at the low-energy edge in
dichloromethane.
Orientation stability of the poled film was also investigated by
the depoling experiments, in which the UVevis spectra of the poled
films are monitored as the films stayed at room temperature in air
b
Onset temperꢁa1ture for weight loss determined from TGA in nitrogen at a heating
rate of 20 ꢂC min
.

4114
Z. Shi et al. / Tetrahedron 67 (2011) 4110e4117
Fig. 3. Some optimized molecular structures with AM1 method.
with the time. After aging for 4 days, the order parameter (F) of the
poled films decreased by 26%, 19%, respectively, for polymers 1/
PMMA and 2a/PMMA (Fig. 6). The result suggests that the side
groups could efficiently block the relaxation of the chromophores
and keep good orientation stability.
3. Conclusions
In this paper, a shape controlling strategy for non-linear optical
chromophores, with terphenyl
p-conjugating bridge, was de-
veloped. On this shape-considering designation, a series of spindle-
like chromophores based on terphenyl group were synthesized. The
measurement results of UVevis spectra demonstrated that the
chromophores are remarkably different from the traditional one
dimensional molecule as the reference compound, which cause
a large blue-shift of the absorption band, and furthermore theoret-
ical calculation demonstrated that the
phores increased with the electro-drawing ability of the substituted
group on the -conjugating bridge. Thermal analysis also indicated
b values of these chromo-
Fig. 4. DSC thermograms of chromophores 2aec, 3bec, 4, and 5.
p
that these chromophores exhibit very good thermal stabilities, the
decomposition temperature even up to 386 ꢂC. Therefore, this
strategy could give a new way to solve the trade-off between non-
linearity and transparency in designing NLO chromophores.
110
100
90
4. Experimental
4.1. Materials
80
70
4
2a
3c
3a
60
50
40
30
20
10
0
Tetrahydrofuran (THF) and 1,4-dioxane were purified by frac-
tional distillation over sodium, Potassium tert-butoxide(Acros Or-
ganics), Tricyanovinyldihydrofuran(TCF), malononitrile, 1,3,3-
trimethyl-5-dicyanovinyl-1-cyclohexene (TDC), and thiophene-2-
boronic acid was prepared according to previous literatures.6,12b
All other solvents and chemical reagents were used as received,
without further purification.
0
100
200
300
400
500
600
700
4.2. Measurements
o
Temperature/ C
Nuclear magnetic resonance (NMR) spectra were measured on
a Bruker AVANCE NMR spectrometer at a resonance frequency of
Fig. 5. TGA curves of chromophore 2a, 3a, 3c, 4 in nitrogen with a heating rate of
20 ꢂC minꢁ1
.

Z. Shi et al. / Tetrahedron 67 (2011) 4110e4117
4115
Table 3
Shows the molecular hyperpolarizabilities (
b
) of the resulting NLO chromophores calculated using the DFT method
1
2a
2b
429.15
2c
438.88
3a
544.35
3b
536.11
3c
562.29
4
5
b0/B3LYP
bvec/B3LYP
bHRS/B3LYP
531.63
434.22
ꢁ386.02
278.17
524.54
552.76
ꢁ493.84
ꢁ383.59
ꢁ388.50
ꢁ511.03
ꢁ501.43
ꢁ527.81
ꢁ432.29
ꢁ433.17
439.58
276.97
281.35
376.24
370.22
388.75
344.77
378.71
0.4
0.3
0.2
0.1
0.0
1.0
0.8
0.6
0.4
0.2
0.0
Before Poling
After Poling
Before Poling
After Poling
26%
decreased
19%
decrease
400
500
600
700
400
500
600
700
Wavelength(nm)
Wavelength(nm)
Fig. 6. UVevis spectra of poled films (1/PMMA, left) compared to the poled films 2a/PMMA (right) varied with time in room temperature. Changes of the order parameter (
were monitored every 10 h for 4 days.
F¼1ꢁAp/A0)
500 MHz for 1H in CDCl3, and TMS was used as internal standard. IR
spectra were taken on an AVATAR 360 FTIR spectrometer. Elemental
analysis was carried out with a FLASH EA 1112 SERIES elemental
analyzer. The molecular weights were determined by high perfor-
mance liquid chromatography-mass spectrometry (HPLCeMS) on
an ANGILENT 1100 LC/MS. Differential scanning calorimeter (DSC)
was performed with NETZSCH 4 at a scan rate of 10 ꢂC/min under
nitrogen. The software of DSC 204 on 18 TASC 414-4 was used to
analyze the DSC curves. The decomposition temperature of the
chromophore samples was analyzed using PerkineElmer TGA 7
thermogravimetric analyzer (TGA) at a heating rate of 10 ꢂC/min in
nitrogen. Thermal degradation temperatures were measured in the
range 50e400 ꢂC. Ultravioletevisible (UVevis) absorption spectra
were measured on an SHIMADZUUV-3100 spectrophotometer.
residual solid was recrystallized in anhydrous ethyl ether to give
the light green solid (7.2 g, 60% yield). Mp¼249 ꢂC. 1H NMR (CDCl3)
d
: 5.36e5.38(d, J¼14 Hz, 2H, CH2), 6.79e6.81(d, J¼8 Hz, 2H, Ph),
6.90e6.93(m, J¼8.5 Hz, 2H, Ph), 6.99e7.03(m, J¼8.5 Hz, 6H, Ph),
7.21e7.24(t, 4H, J¼8.5, 7.5 Hz, Ph), 7.62e7.66(t, J¼7.5 Hz, 6H, Ph),
7.75e7.79(t, 9H, J¼7.5 Hz, Ph). 13C NMR (125 MHz, CDCl3, TMS):
d
(ppm) 149.75, 145.91, 137.43, 136.26, 129.94, 129.65, 128.88,
128.71, 127.93, 126.98, 125.74, 50.14.
4.4.2. 2,5-Dibromobenzene-1,4-dicarbaldehyde (7). The reference
method12a was modified using the p-xylene as starting material,
resulted white solid (7.53 g, 96%). Mp¼192e193 ꢂC. 1H NMR(CDCl3):
d
10.35 (s, 2H), 8.16 (s, 2H). MS (ESI), m/z: 291.0 [MþH]þ. 13C NMR
(125 MHz, CDCl3, TMS):
d (ppm) 189.81, 137.27, 134.94, 125.47.
4.4.3. 2,5-Terphenyl-dicarbaldehyde (8a). Triphenyl phosphine
(0.015 g, 0.06 mmol), palladium acetate (0.002 g, 0.01 mol), phe-
nylboronic acid (0.24 g, 2 mmol), and 7 (0.29 g,1 mmol) were added
into a flask. A degassed mixture of isopropyl alcohol (10 ml), so-
dium carbonate (aq) (2 N/L, 3 ml), and water (1 ml) was transferred
onto the solids, and the resulting solution was stirred under reflux
at 70 ꢂC for 4 h. The crude product was extracted with dichloro-
methane and washed with aq NaHCO3. The organic layer was
concentrated under vacuum and purified by column chromatog-
raphy on silica gel eluting with petroleum/ethyl acetate (30:1) to
give white crystals (0.27 g, 95%). 1H NMR (500 MHz, CDCl3, TMS):
4.3. Poling conditions
For studying the properties of chromophores in polymer ma-
terials, guestehost polymers were generated by mixing com-
pounds 1 or 2a (25 wt %) with poly(methylmethacrylate) (PMMA)
using 1,1,2,2-tetrachloroethane as the solvent, the resulting solu-
tions were filtered through 0.2
spin coated onto precleaned indium tin oxide (ITO) glass substrates.
mm Teflon syringe filters and were
A film thickness of 2.0ꢃ0.5
mm was obtained by using a spin rate in
the range 850e1000 rpm. After baking at 60 ꢂC under vacuum for
6e12 h in order to remove the solvent, the films were wire poled
using a tungsten wire held parallel to and above the films (at
a distance of 1 cm) under a poling field of 3.0 kV at 80 ꢂC.
d
(ppm) 7.44e7.46(d, 4H, J¼9.5 Hz, Ar), 7.50e7.53 (t, 6H, J¼9.5 Hz,
Ar), 8.11(s, 2H, Ar), 10.09(s, 2H, CHO). IR (KBr, cmꢁ1): 1665 (eCHO).
13C NMR (125 MHz, CDCl3, TMS):
(ppm) 189.42, 150.17, 131.59,
130.47, 124.05, 123.91, 123.52, 121.74.
d
4.4. Synthesis
4.4.4. 2,5-(40,400-Dimethoxy)-terphenyl-dicarbaldehyde
procedure for 8a was repeated with 4-methoxyphenylboronic acid
(8b). The
4.4.1. (4-Diphenylamino)triphenylphosphorusbromide (6). To a solu-
tion of triphenylamine(4.9 g, 20 mmol) in N,N-dimethyl formamide
(DMF) (50 ml) was added POCl3 (1.2 mL), the solution was stirred
under ice-bath condition for 10 min. The reaction mixture was
heated to 90 ꢂC and stirred for 4 h. After cooling down to room
temperature, the mixture was extracted with ethyl acetate three
times. After evaporating the solvent, the mixture was added so-
dium borohydride in absolute ethanol (50 mL) and reacted for 2 h.
After removing the solvent, the residue was added triphenyl
phosphorus hydrobromide (6.86 g, 20 mmol) in CHCl3. The solution
was heated to reflux for 2 h. After removing the solvent, the
(0.3 g, 2 mmol) and a reaction time of 12 h resulting a yellow crystal
(0.29 g, 85%). 1H NMR (500 MHz, CDCl3, TMS):
d (ppm) 7.03e7.05(d,
4H, J¼8.5 Hz, Ar), 7.35e7.37 (t, 4H, J¼8.5 Hz, Ar), 8.06(s, 2H, Ar),
10.08(s, 2H, CHO). IR (KBr, cmꢁ1): 1660 (eCHO). 13C NMR (125 MHz,
CDCl3, TMS):
d (ppm) 191.06, 159.05, 142.74, 135.47, 130.27, 129.10,
127.70, 113.21, 54.39.
4.4.5. 2,5-(40,400-Ditrifluoromethyl)-terphenyl-dicarbaldehyde
(8c). The procedure for 8a was repeated with 4-(trifluoromethyl)

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Z. Shi et al. / Tetrahedron 67 (2011) 4110e4117
phenylboronic acid (0.38 g, 2 mmol) and a reaction time of 12 h.
Resulting a yellow crystal (0.34 g, 80%). 1H NMR (500 MHz, CDCl3,
(CN)2), 6.97e6.99(d, 2H, J¼8 Hz, Ar), 7.00e7.05(m, 2H, CH]C),
7.06e7.09(d, 1H, J¼16 Hz, CH]C), 7.12e7.15(d, 1H, J¼16 Hz, CH]C),
7.35e7.38(dd, 6H, J¼8 Hz, Ar), 7.45e7.46(d, 4H, J¼8 Hz, Ar), 7.68(s,
TMS):
d
(ppm) 7.58e7.59(d, 4H, J¼8 Hz, Ar), 7.80e7.82 (t, 4H,
J¼8 Hz, Ar), 8.12(s, 2H, Ar), 10.06(s, 2H, CHO). IR (KBr, cmꢁ1): 1677
1H, Ar), 7.69(s, 1H, Ar). 13C NMR (125 MHz, CDCl3, TMS):
d (ppm)
(eCHO). 13C NMR (125 MHz, CDCl3, TMS):
d
(ppm) 189.50, 142.55,
159.25, 154.32, 140.91, 139.83, 137.35, 135.99, 132.40, 131.35, 131.26,
131.18, 130.97, 130.91, 130.09, 130.01, 129.44, 128.19, 127.91, 127.34,
126.30, 123.29, 113.75, 90.34, 55.42, 42.92, 39.01, 31.98, 29.68, 27.97.
MS (ESI), m/z: 632.3 [MþH]þ. Anal. Calcd for C43H41N3O2: C, 81.74;
H, 6.54; N, 6.65. Found: C, 81.65; H, 6.41; N, 6.77.
138.89, 135.53, 130.24, 129.55, 129.29, 124.80, 123.92.
4.4.6. 2,5-Di(thiophen-2-yl)-terphenyl-dicarbaldehyde
(8d). The
procedure for 8a was repeated with thiophene-2-boronic acid
(0.25 g, 2 mmol) and a reaction time of 5 h. Resulting a yellowcrystal
(0.27 g, 90%). 1H NMR (500 MHz, CDCl3, TMS):
d
(ppm) 7.14e7.15(d,
4.5.3. 2-(3-(4-(4-(Dimethylamino)styryl)-2,5-(40,400-ditri-
fluoromethylphenyl)styryl)-5,5-dimethylcyclohex-2-enylidene)malo-
nonitrile (2c). Yield (0.56 g, 79%). Mp¼221e225 ꢂC; IR (KBr, cmꢁ1):
2H, J¼5 Hz, thienyl), 7.19e7.21 (t, 2H, J¼5, J¼4 Hz, thienyl),
7.54e7.55(d, 2H, J¼5 Hz, thienyl), 8.16(s, 2H, Ar),10.27(s, 2H, CHO). IR
(KBr, cmꢁ1): 1680(eCHO). 13C NMR (125 MHz, CDCl3, TMS):
d
(ppm)
2220 (eCN). 1H NMR (500 MHz, CDCl3, TMS):
d (ppm) 1.02 (s, 6H),
191.54, 137.76, 137.37, 128.52, 128.73, 130.49, 131.26, 137.17.
2.21 (s, 2H), 2.56 (s, 2H), 3.11(s, 6H), 6.84(s, 1H, CH]C (CN)2),
6.99e7.0(d, 2H, J¼5.5 Hz, Ar), 7.01e7.05(d, 1H, J¼16 Hz, CH]CH),
7.09e7.13(d, 1H, J¼16 Hz, CH]CH), 7.42e7.46(m, 2H, J¼16 Hz, CH]
CH), 7.56e7.59 (m, 6H, Ar), 7.71 (s, 1H, Ar), 7.72(s, 1H, Ar),
7.77e7.79(dd, 4H, J¼8 Hz, Ar). 13C NMR (125 MHz, CDCl3, TMS):
4.4.7. 2-[4-(N,N-dimethylamino)styryl]-1,4-diphenylbenzaldehyde
(9a). Terphenyl-1,4-dicarbaldehyde 8a (0.60 g, 2 mmol) and 4-(N,N-
dimethylamino)benzyltriphenyl phosphonium iodide (1.05 g,
2 mmol) were dissolved in anhydrous dichloromethane (50 ml),
a solution of potassium tert-butoxide (0.34 g, 3 mmol) in anhydrous
dichloromethane (10 ml) were added, and the mixture was then
allowed to stir for 2 h at room temperature. After filtration, the fil-
trate was evaporated then purified by column chromatography on
silica gel eluting with petroleum/ethyl acetate (15:1). An orange
crystalline compound was then obtained by recrystallization in aq
ethanol (0.52 g, 64%). Mp¼173e174 ꢂC. IR (KBr, cmꢁ1): 1668 (eCHO).
d
(ppm) 170.36, 168.95, 159.75, 143.60, 137.36, 134.15, 130.60,
130.08,128.25,128.04,127.38,125.39,125.34,124.04,120.52,113.34,
113.15, 112.59, 112.37, 78.16, 42.85, 38.92, 32.32, 29.66, 27.92. MS
(ESI), m/z: 708.2 [MþH]þ. Anal. Calcd for C43H35F6N3: C, 72.97; H,
4.98; N, 5.94. Found: C, 72.78; H, 4.76; N, 6.06.
4.5.4. 2-(3-Cyano-(4-(4-(dimethylamino)styryl)-2,5-diphenylstyryl)
5,5-dimethylfuran-2(5H)-ylidene)malononitrile
powder(0.46 g, 78%). IR (KBr, cmꢁ1): 2226 (eCN). 1H NMR
(500 MHz, CDCl3, TMS): (ppm) 1.25 (s, 6H), 3.02 (s, 6H), 6.67e6.68
(3a). Deep
red
1H NMR (CDCl3, 500 MHz)
d
2.98 (s, 6H), 6.68 (d, J¼9.0 Hz, 2H), 6.96
(d, J¼16 Hz, 1H), 7.20 (d, J¼16 Hz, 1H), 7.34 (d, J¼9.0 Hz, 2H), 7.40(d,
d
J¼9.5 Hz, 2H), 7.46(d, J¼8 Hz, 4H), 7.52 (t, J¼8 Hz, 6H), 7.79 (s, 1H),
(d, 2H, J¼8 Hz), 6.98e7.01 (d, 1H, J¼16 Hz, CH]CH), 7.18 (d, 1H,
J¼16 Hz, CH]CH), 7.29e7.31 (d, 2H, Ar, J¼8 Hz), 7.36e7.37 (d, 2H,
J¼8 Hz), 7.43e7.46 (d, 1H, J¼16 Hz, CH]CH), 7.45e7.48 (m, 3H,
CH]CH, Ar), 7.49e7.55 (m, 6H, Ar), 7.75 (s, 1H, Ar), 7.83 (s, 1H, Ar).
7.99(s, 1H), 9.99 (s, 1H). 13C NMR (125 MHz, CDCl3, TMS):
d (ppm)
191.69, 149.76, 134.98, 134.64, 134.01, 133.77, 133.65, 131.46, 131.39,
130.12,129.95,129.80,129.64,117.61,116.48,111.74,111.55, 39.72. MS
(ESI), m/z: 404.1 [MþH]þ. Anal. Calcd for C29H25NO: C, 86.32; H, 6.24;
N, 3.47. Found: C, 86.45; H, 6.33; N, 3.55.
13C NMR (125 MHz, CDCl3, TMS):
d (ppm) 158.51, 150.60, 144.08,
141.98, 140.16, 138.99, 138.38, 133.53, 132.97, 132.45, 131.44, 130.31,
130.16, 129.97, 129.72, 128.78, 128.62, 128.48, 128.38, 127.77, 127.00,
121.07, 112.20, 111.93, 80.97, 48.99, 40.17, 29.64. MS (ESI), m/z: 585.2
[MþH]þ. Anal. Calcd for C40H32N4O: C, 82.17; H, 5.52; N, 9.58.
Found: C, 82.05; H, 5.65; N, 9.63.
4.5. General procedure for the synthesis of compound 2e5
Compound 9 (1 equiv) was dissolved in THF, 3-dicyano-
methylene-1,5,5-trimethylcyclohexene
or
Tricyanovinyldihy-
drofuran (1.1 equiv) and piperidine (cat. amount) were added, and
the stirred mixture was then heated to reflux for 2 h. A purple
solution was obtained. It was then poured into water. The crude
dark precipitate was collected by filtration. The product was puri-
fied by column chromatography on silica gel eluting with petro-
leum/ethyl acetate.
4.5.5. 2-(3-Cyano-(4-(4-(dimethylamino)styryl)-2,5-(40,400-dime-
thoxyphenyl)styryl)5,5-dimethylfuran-2(5H)-ylidene)malononitrile
(3b). Red powder (0.42 g, 65%). IR (KBr, cmꢁ1): 2227 (eCN). 1H
NMR (500 MHz, CDCl3, TMS): d(ppm) 1.25 (s, 6H), 3.01 (s, 6H), 3.90
(s, 6H), 6.77e6.78 (d, 2H, J¼8 Hz), 7.01e7.06 (m, 5H, J¼8.5 Hz, Ar,
CH]CH), 7.16e7.19 (d, 1H, J¼16 Hz, CH]CH), 7.26e7.29 (m, 3H,
J¼16 Hz, Ar, CH]CH), 7.32e7.35 (m, 3H, Ar, CH]CH), 7.38e7.40 (d,
2H, J¼8.5 Hz, Ar), 7.77 (s,1H, Ar), 7.78 (s,1H, Ar). 13C NMR (125 MHz,
4.5.1. 2-(3-(4-(4-(Dimethylamino)styryl)-2,5-diphenylstyryl)-5,5-di-
methylcyclohex-2-enylidene)malononitrile
(2a). Red
powder
CDCl3, TMS): d (ppm) 160.02, 159.26, 158.91, 143.57, 142.06, 139.61,
(0.30 g, 53%). Mp¼221e224 ꢂC. IR (KBr, cmꢁ1): 2219 (eCN). 1H NMR
133.19, 131.43, 131.17, 130.96, 130.69, 130.28, 128.32, 127.07, 121.57,
114.42, 113.95, 113.23, 112.16, 80.62, 55.46, 55.34, 40.29, 29.69. MS
(ESI), m/z: 645.2 [MþH]þ. Anal. Calcd for C42H36N4O3: C, 78.24; H,
5.63; N, 8.69. Found: C, 77.96; H, 5.72; N, 8.81.
(500 MHz, CDCl3, TMS): d(ppm) 0.98 (s, 6H), 2.19 (s, 2H), 2.51 (s,
2H), 2.93(s, 6H), 6.64e6.66(d, 2H, J¼7 Hz), 6.78(s, 1H, CH]C(CN)2),
6.94e6.98(m, 2H, Ar), 7.06e7.13(dd, 2H, J¼16 Hz), 7.27e7.28(d, 1H,
CH]CH), 7.36e7.37 (d, 1H, CH]CH), 7.44e7.52(m, 10H, Ar), 7.68 (s,
1H, Ar), 7.73(s, 1H, Ar). 13C NMR (125 MHz, CDCl3, TMS):
d
(ppm)
4.5.6. 2-(3-Cyano-(4-(4-(dimethylamino)styryl)-2,5-(40,400-di-tri-
fluoromethyl)phenylstyryl) 5,5-dimethylfuran-2(5H)-ylidene)malo-
nonitrile (3c). Deep red powder (0.59 g, 82%). IR (KBr, cmꢁ1): 2220
169.05, 154.25, 150.17, 141.49, 140.13, 137.37, 135.76, 131.71, 130.84,
129.78, 128.24, 128.10, 128.04, 127.80, 127.61, 127.49, 127.04, 126.93,
125.43, 123.18, 121.98, 113.58, 112.19, 77.95, 42.83, 40.35, 38.90,
31.85, 27.86. MS (ESI), m/z: 572.3 [MþH]þ. Anal. Calcd for C41H37N3:
C, 86.13; H, 6.52; N, 7.35. Found: C, 86.06; H, 6.61; N, 7.43.
(eCN). 1H NMR (500 MHz, CDCl3, TMS):
d(ppm) 1.25 (s, 6H), 3.00 (s,
6H), 6.77 (m, 2H, Ar), 6.86e6.89 (d,1H, CH]CH, J¼16 Hz), 7.19e7.23
(dd, 2H, J¼16 Hz, CH]CH), 7.28e7.30 (m, 3H, Ar, CH]CH),
7.50e7.51 (d, 2H, J¼7.5 Hz, Ar), 7.58e7.60 (d, 2H, J¼8 Hz, Ar), 7.66 (s,
1H, Ar), 7.76e7.77 (d, 2H, Ar, J¼8.5 Hz), 7.81e7.83 (m, 3H, Ar). 13C
4.5.2. 2-(3-(4-(4-(Dimethylamino)styryl)-2,5-(40,400-dimethox-
yphenyl)styryl)-5,5-dimethyl cyclohex-2-enylidene)malononitrile
(2b). Yield (0.51 g, 81%). Mp¼271e273 ꢂC; IR (KBr, cmꢁ1): 2218
NMR (125 MHz, CDCl3, TMS): d (ppm) 157.33, 143.09,142.55,142.23,
141.88, 139.21, 138.07, 134.79, 130.47, 130.18, 130.07, 128.58, 127.34,
127.17, 126.79, 126.00, 125.95, 125.90, 125.67, 125.62, 119.90, 113.82,
112.88, 112.16, 90.37, 82.30, 40.23, 29.69. MS (ESI), m/z: 721.2
(eCN). 1H NMR (500 MHz, CDCl3, TMS):
d (ppm) 1.02 (s, 6H), 2.25(s,
2H), 2.56 (s, 2H), 3.12(s, 6H), 3.91(s, 6H, OCH3), 6.81(s, 1H, CH]C

Z. Shi et al. / Tetrahedron 67 (2011) 4110e4117
4117
[MþH]þ. Anal. Calcd For C42H30F6N4O: C, 69.99; H, 4.20; N, 7.77.
69, 5077; (h) Lee, S. H.; Park, J. R.; Jeong, M.-Y.; Kim, H. M.; Li, S.; Song, J.; Ham, S.;
Jeon, S.-J.; Cho, B. R. ChemPhysChem 2006, 7, 206.
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Chem. 2004, 76, 1421; (c) Briers, D.; Picard, I.; Samyn, C. Macromol. Rapid
Commun. 2003, 24, 841.
3. (a) Kajzar, F. L.; Jen, A. K.-Y. Adv. Polym. Sci. 2003, 161, 1; (b) Li, Q.; Li, Z.; Zeng, F.;
Gong, W.; Li, Z.; Zhu, Z.; Ye, C.; Qin, J. J. Phys. Chem. B 2007, 111, 508; (c) Lee, G.
Y.; Jang, H. N.; Lee, J. Y. J. Polym. Sci., Part A: Polym. Chem. 2008, 46, 3078; (d) Bai,
Y.; Song, N.; Gao, J.; Sun, X.; Wang, X.; Yu, G.; Wang, Z. Y. J. Am. Chem. Soc. 2005,
127, 2060; (e) Centore, R.; Riccio, P.; Fusco, S.; Carella, A.; Quatela, A.; Schutz-
mann, S.; Stella, F.; De Matteis, F. J. Polym. Sci., Part A: Polym. Chem. 2007, 45,
2719.
4. (a) Moylan, C.; Twieg, R.; Lee, V. Y.; Swanson, S.; Betterton, K.; Miller, R. J. Am.
Chem. Soc. 1993, 115, 12599; (b) Ermer, S.; Lovejoy, S.; Leung, D. S.; Warren, H.
Chem. Mater. 1997, 9, 1437; (c) Zhang, H.; Lu, D.; Peyghambarian, N.; Fallahi, M.;
Luo, J.; Chen, B.; Jen, A. K.-Y. Opt. Lett. 2005, 30, 117; (d) Rao, V. P.; Wong, K. Y.;
Jen, A. K.-Y.; Drost, K. Chem. Mater. 1994, 6, 2210.
Found: C, 69.86; H, 4.32; N, 7.87.
4.5.7. 2-(3-(4-(4-(Diphenylamino)styryl)-2,5-(40,400-dimethoxyphenyl)
styryl)-5,5-dimethyl cyclohex-2-enylidene)malononitrile (4). Yield
(0.57 g, 76%). Mp¼170e172 ꢂC. IR (KBr, cmꢁ1): 2219 (eCN). 1H NMR
(500 MHz, CDCl3, TMS): d (ppm) 1.01 (s, 6H), 2.22 (s, 2H), 2.54 (s, 2H),
3.89(s, 6H), 6.81 (s, 1H, CH]C(CN)2), 6.93e7.11(m, 15H, CH]CH, Ar),
7.13e7.16 (d, 1H, J¼15 Hz, CH]CH), 7.19e7.25 (m, 6H, J¼8.5 Hz, Ar),
7.35e7.37(d, 2H, J¼8.5 Hz), 7.38e7.39 (d, 2H, J¼8.5 Hz, Ar), 7.45e7.46
(d, 1H, J¼9 Hz, Ar), 7.66 (s, 1H, Ar), 7.69(s,1H, Ar). 13C NMR (125 MHz,
CDCl3, TMS):
d (ppm) 169.11, 159.04, 154.17, 147.38, 146.78, 140.80,
139.83, 137.14, 136.00, 132.32, 132.12, 130.78, 130.44, 129.80, 129.56,
129.16, 128.41, 128.10, 127.74, 127.40, 124.94, 124.49, 124.25, 123.24,
122.87, 113.65, 112.68, 55.22, 42.79, 38.89, 31.86, 29.51, 27.83. MS
(ESI), m/z: 756.3 [MþH]þ. Anal. Calcd for C53H45N3O2: C, 84.21; H,
6.00; N, 5.56. Found: C, 84.17; H, 5.86; N, 5.69.
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4.5.8. 2-(3-(4-(4-(Diphenylamino)styryl)-2,5-di(thiophen-2-yl)
styryl)-5,5-dimethylcyclo hex-2-enylidene)malononitrile (5). Yield
(0.58 g, 82%). Mp¼226e229 ꢂC. IR (KBr, cmꢁ1): 2219 (eCN). 1H NMR
(500 MHz, CDCl3, TMS):
d (ppm) 1.02 (s, 6H), 2.16 (s, 2H), 2.50 (s,
2H), 6.86(s, 1H, CH]C(CN)2), 6.92e6.95 (d, 1H, J¼16 Hz, CH]CH),
7.04e7.13 (m, 14H, CH]CH, Ar), 7.16e7.18 (t, 2H, J¼3.5 Hz, thienyl),
7.23e7.25(d, 2H, J¼8.5 Hz, Ar), 7.27e7.29 (d, J¼8.5 Hz, 2H, Ar),
7.32e7.35(d, 1H, J¼16 Hz, CH]CH), 7.41e7.43(d, 2H, J¼8.5 Hz, Ar),
7.46e7.47(d, 2H, J¼8.5 Hz, Ar), 7.72 (s, 1H, Ar), 7.91(s, 1H, Ar). 13C
NMR (125 MHz, CDCl3, TMS): d (ppm) 168.95,153.52,147.25,140.56,
138.07, 133.94, 132.2, 130.92, 129.34, 128.21, 128.02, 127.92, 127.7,
127.62, 126.88, 124.82, 124.68, 124.19, 124.1, 123.4, 123.32, 123.25,
123.08, 122.87, 113.4, 79.13, 45.64, 39.14, 31.99, 29.68, 27.98. MS
(ESI), m/z: 708.2 [MþH]þ. Anal. Calcd for C47H37N3S2: C, 79.74; H,
5.27; N, 5.94. Found: C, 79.87; H, 5.35; N, 6.03.
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4.6. Computational details
Geometrical optimization of our studied compound without
any symmetry constraint was carried out with the B3LYP combi-
nations of density functional theory (DFT) in the Gaussian 03
computational chemistry program.22 The B3LYP functional is
a combination of Becke’s three-parameter hybrid exchange func-
tional23 and the LeeeYangeParr24 correlation functional. Basis sets
of 6-31G were applied to our studied compounds. The first-order
*
hyperpolarizabilities were calculated by using the finite-field (FF)
method.25
Acknowledgements
13. Ma, X.; Liang, R.; Yang, F.; Zhou, Q.; Song, N.; Zhang, J. J. Mater. Chem. 2008, 18,
1756.
14. Davies, J.; Elangovan, A.; Sullivan, P.; Olbricht, B.; Bale, D.; Li, X.; Dalton, L. J. Am.
Chem. Soc. 2008, 130, 10565.
15. Tannaci, J.; Noji, M.; McBee, J.; Tilley, T. J. Org. Chem. 2008, 73, 7895.
16. Li, Q.; Lu, C.; Zhu, J.; Fu, E.; Zhong, C.; Li, S.; Cui, Y.; Qin, J.; Li, Z. J. Phys. Chem. B
2008, 112, 4545.
This work was supported by National Natural Science Foundation
of China (No. 20974036; 20903020), the Science and Technology
Development Project Foundation of Jilin Province (20090317), the
Project-sponsored by SRF for ROCS, and the Training Fund of NENU’s
Scientific Innovation Project (NENU-STC08005).
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