Facile Preparation of α-Cyano-α,ω-Diaryloligovinylenes: A New Class of Color-Tunable Solid Emitters

Article abstract of DOI:10.1002/asia.201500473

An efficient Knoevenagel condensation reaction was used to construct a series of α-cyano-α,ω-diaryloligovinylenes, which show prominent fluorescence emission in the solid state. On investigating the effect of conjugation length on fluorescent properties,

Full text of DOI:10.1002/asia.201500473

DOI: 10.1002/asia.201500473
Full Paper
Fluorescence
Facile Preparation of a-Cyano-a,w-Diaryloligovinylenes: A New
Class of Color-Tunable Solid Emitters
Peng An, Nian-Sheng Xu, Hao-Li Zhang, Xiao-Ping Cao,* Zi-Fa Shi,* and Wei Wen[a]
Abstract: An efficient Knoevenagel condensation reaction
was used to construct a series of a-cyano-a,w-diaryloligo-
vinylenes, which show prominent fluorescence emission in
the solid state. On investigating the effect of conjugation
length on fluorescent properties, we found that the diene
structure showed superior solid-state luminescence. Further-
more, the emission color could be adjusted by introducing
donor or acceptor functional groups at the terminal aryl
groups. Full-color emission in the visible region can be ach-
ieved by adding different functional groups to the a-cyano-
a,w-diaryldivinylene moiety. The structure–property relation-
ships were elucidated and some observations such as the
substitution position effects were discussed. These com-
pounds have potential applications as full-color solid emis-
sive candidates in material science and their simple struc-
tures allow them to be easily modified resulting in further
interesting properties.
tons and color tunable emission are still limited.[8] Herein, we
report the preparation of solid-state color-tunable emitters by
Introduction
Organic chromophores exhibiting efficient solid-state lumines-
cence are strongly desired for practical applications such as or-
ganic light-emitting diodes (OLEDs), organic light-emitting
field-effect transistors (OLEFETs), and organic solid-state
lasers.[1] The design and synthesis of solid-emissive organic
molecules remains a difficult task because it is necessary to
conquer the commonly observed aggregation-caused quench-
ing (ACQ) effect in the solid state.[2] Furthermore, motivated by
the commercial potentials of full-color displays[3] and white-
lighting emission,[4] it is highly desirable to realize multicolor
emission with molecular mixtures of similar chemical struc-
tures. This is because it is relatively straightforward to obtain
a series of structurally similar compounds with tunable emis-
sion by simple synthetic modification. Furthermore, micro-
phase segregation, a detrimental problem in device per-
formance owing to the mixing of emitting materials with sig-
nificantly different chemical structures, can also be avoided
with structurally similar analogues.[4b,5]
derivatizing cyano-substituted stilbenes to a homologous
series of a-cyano-a,w-diaryloligovinylene compounds 5a–5 f,
6a–6i, and 7a–7 f with tunable fluorescent emitting bands
(Table 1). In designing such multicolor solid-state emission
structures, the following factors were taken into consideration:
(i) the substituted (E)-diphenylethene segment is commonly
found in AIE active structures;[2b,6b,9] (ii) introducing donor or
Table 1. Synthesis and structures of compounds 5a–5 f, 6a–6i, and 7a–
7 f.
The “aggregation-induced emission (AIE)” term was coined
by the research group of Tang[6] and this unleashed a flurry of
researches in the discovery of solid-emissive fluorophores.[2b,7]
However, similar structures with both cognate chemical skele-
Yield [%]
R
R’
[a] Dr. P. An,+ N.-S. Xu,+ Prof. H.-L. Zhang, Prof. X.-P. Cao, Dr. Z.-F. Shi, W. Wen
State Key Laboratory of Applied Organic Chemistry
College of Chemistry and Chemical Engineering
Lanzhou University
Lanzhou, 730000 (P. R. China)
E-mail: caoxplzu@163.com
[+] These authors contributed equally to this work.
5a (70)
5b (68)
5c (72)
5d (66)
5e (48)
5 f (55)
6a (82)
6b (77)
6c (81)
6d (85)
6e (78)
6 f (82)
6g (73)
6h (68)
6i (66)
7a (72)
7b (76)
7c (70)
7d (70)
7e (61)
7 f (65)
H
OCH3
H
OCH3
OCH3
NO2
NEt2
CH3
NPh2
H
H
OCH3
OCH3
NO2
OCH3
H
H
H
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/asia.201500473.
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ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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acceptor substituents to the terminal aryl rings
is a facile way to obtain an emission wave-
length shift by adjusting the energy gap or
varying the degree of intramolecular charge
transfer;[9] (iii) ethylene is the smallest p unit
and introducing further vinylene units in the
conjugation skeleton can generate a significant
bathochromic shift of fluorescent emission;[10]
(iv) the cyano group might not only render
ground and excited states more distinct to
produce large Stokes shift by desymmetriza-
tion of diphenylalkenes, but restrict intramo-
lecular motions through a supramolecular CÀ
H···N hydrogen-bond interaction in the solid or
crystal state.[11]
Table 2. Photophysical properties of samples 5a–5 f, 6a–6i, and 7a–7 f as an amorphous
powder and in solution.
Samples lmax [nm][a] band
Solid[c]
Solution[f]
gap
[eV][b]
lem [nm][d] Stokes
Ff [%][e] lem [nm][d] Stokes
Ff [%][e]
shift [cmÀ1
]
shift [cmÀ1
]
[g]
5a
5b
5c
5d
5e
5 f
6a
6b
6c
6d
6e
6 f
6g
6h
6i
313
333
320
328
357
359
338
358
365
368
396
394
422
339
417
370
381
390
395
408
425
3.55 ND
–
ND
ND
ND
430
507
ND
ND
ND
–
–
–
–
7.5
–
–
–
–
3.33 425
3.36 ND
3.27 412
2.92 590
2.87 565
3.22 465
3.05 490
2.94 495
2.92 485
2.72 590
2.64 614
2.62 572
3.21 479
2.61 540
2.92 526
2.84 518
2.72 538
2.71 564
2.59 635
2.43 684
6501
44.2
–
28.4
1.9
25.2
14.3
70.2
0.8
53.0
13.2
1.9
45.2
30.9
25.5
0.86
13.0
5.55
0.6
6216
11 062
10156
8080
7525
7195
6555
8303
9093
6214
8621
5462
8016
6942
7053
7586
8762
8910
7231
8287
470
ND
6121
–
522
567
510
400
549
506
507
544
538
553
631
6095
7744
4089
4499
5766
7264
6523
7259
6729
6427
7682
62.1
3.0
78.0
3.2
69.3
–
–
–
–
91.7
–
Results and Discussion
Synthesis
7a
7b
7c
7d
7e
7 f
By combining all the considerations above, we
synthesized the target compounds 5a–5 f,
6a–6i, and 7a–7 f through a Knoevenagel
condensation reaction. Hence, p-substituted 2-
phenylacetonitrile 1a–1 f and the p-substitut-
ed aromatic aldehyde 2a–2c, 3a–3c, and 4a–
4c were converted into a-cyano-a,w-diaryl-
oligovinylene 5a–5 f, 6a–6i, and 7a–7 f in 48–
85% yields in the presence of catalytic
amount of NaOCH3 (0.05–0.10 equiv) at room
0.4
0.23
[a] Measured in EtOH (10 mm). [b] Calculated from UV/Vis absorption. [c] Measured using
amorphous powder. [d] 368–454 nm was used as excitation wavelength based on excitation
spectrum of each compound. [e] Absolute quantum yield. [f] Measured in THF (10 mm).
[g] Quantum yield was not measured because of low fluorescence. ND=fluorescence not
detectable.
temperature with only Z configuration (Table 1). The products
could be easily obtained by recrystallization and filtration. For
compounds 5–7, besides parent compound (a), one donor (b
and c), two donors (d), and donor–p–acceptor (D–p–A) type (e
and f) structures were synthesized, respectively, with selective
donor and acceptor groups such as -OCH3 and -NO2. Substrates
4a–4c were synthesized from 3a–3c through a Wittig reac-
tion, then reduced with diisobutylaluminum hydride (DIBAL-H),
and subsequently oxidized with Dess–Martin periodinane
(Scheme 1).
absorption wavelength ranges from 313 nm to 425 nm, and
both extension of conjugation length with additional double
bond(s) and incorporation of electron-donating or electron-
withdrawing functional groups could contribute to the absorp-
tion bathochromic shift. This broad scope of absorbance is
indeed favorable for shifting the emission wavelength. Accord-
ingly, the band gap energy became narrower with additional
conjugation or by introducing donor–acceptor functional
groups (Table 2). The D–p–A substitution pattern showed the
largest bathochromic absorbance and smallest band gap
energy.
Next, the fluorescence properties including fluorescence
emission and fluorescence quantum yield were investigated
both in amorphous powder and in diluted solution (Table 2). In
brief, this series of a-cyano-a,w-diaryloligovinylenes exhibited
an AIE effect. Most samples showed significant fluorescent
emission in the solid state. However, most compounds showed
very weak or almost no fluorescence in diluted solution be-
cause of the flexible p systems except several D–p–A type
compounds 5e, 6e, 6g, 6i, and 7e. The maximum emission
wavelengths of the solid powder extend from 412 nm (5d) to
684 nm (7 f) with large Stokes shifts (Table 2, 5462–
11 062 cmÀ1). To our delight, the fluorescence emission range
of these a-cyano-a,w-diaryloligovinylene derivatives in the
solid state covered the whole visible region.
Photophysical Properties
With all the samples in hand, the UV/Vis absorptions were first
measured in diluted solution (Table 2, see Figure S1–S3 in the
Supporting Information). It was observed that the maximum
The fluorescence characteristics are summarized: (i) The ho-
mologous series with one ethylene unit distinction displayed
Scheme 1. Synthesis of substrates 4a–4c.
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a large difference in luminous efficiency. For the three conju-
gated groups, the diene (except 6c and 6 f) gave superior lu-
minous efficiency compared to that of the monoene and
triene derivatives in most cases (for example, compound 5a
was not fluorescent in the solid state, while compound 6a
showed blue emission with a fluorescence quantum yield of
14.3%, and the emissive efficiency of 7a was reduced to less
than 1%), which suggests that conjugation length is important
for high-efficiency fluorescence for this type of compound.
Therefore, full-color solid emission in the visible region was
achieved by simply modifying the diene skeleton with donors
or acceptors (Figure 1 and Figure S5, see the Supporting Infor-
mation). (ii) Regioisomers were found to show dramatically dif-
ferent fluorescent efficiency. The structures with one donor
The corresponding frontier orbital levels of the three com-
pounds were estimated by DFT calculation based on crystal
structure data (Figure 5 and Figure S11, see the Supporting In-
formation).
The crystal structure of compound 6b is shown in Figure 2
and Figure S8 (see the Supporting Information). It was found
that the whole p conjugated skeleton displayed a slightly
twisted framework, and from the side view (Figure 2b), the di-
hedral angles between two phenyl rings and diene fragment
Figure 2. a) Single crystal structure of compound 6b from the b) side view
and c) packing view. d) The CÀH···N hydrogen-bond interaction in crystal
packing.
Figure 1. a) Photographs of samples 6a, 6b, 6i, and 6d–6g (amorphous
powder) under 365 nm UV light. b) Normalized fluorescence spectra of cor-
responding samples in the solid state.
group (-OCH3) connected to the phenyl ring (Table 1) had dif-
ferent fluorescent efficiencies (comparison of compounds 5b,
6b, and 7b to 5c, 6c, and 7c respectively). The high fluores-
cence quantum yield could be maintained when the -OCH3
was changed to an electron-donating group such as -NEt2,
-CH3, -NPh2 (6g, 45.2%; 6h, 30.9%; 6i, 25.5%). (iii) The D–p–A
type structures exhibited long wavelength emission with de-
creased fluorescence quantum yields; some of them were
strongly fluorescent in dilute solution (compounds 5e, 6e, 6i,
and 7e).
Figure 3. a) Single crystal structure of compound 6c from the b) side view
and c) packing view.
Analysis of Structure–Property Relationships
To understand the above emission features of these com-
pounds and better tune the fluorescence properties, com-
pounds 6b, 6c, and 6e were crystallized in a CH2Cl2/hexane
mixed solvent[12] to afford single crystals[7d] and subsequently
subjected to X-ray crystallographic analysis (Figure 2–4, see
Figure S8–S10 and Table S1 in the Supporting Information).
Figure 4. a) Single crystal structure of compound 6e from the b) side view
and c) packing view.
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solid state was shifted to orange region (lem =590 nm). The
single crystal structure revealed that the p-skeleton of com-
pound 6e had an essentially planar configuration and lamellar
stacking was formed in space (Figure 4 and Figure S10 in the
Supporting Information). Furthermore, different types of supra-
molecular interactions were detected. First, O···N and O···H in-
teractions were observed in nitro-nitro groups and nitro-me-
thoxy groups, and the interaction distances were 2.94 Š and
2.70 Š, respectively. Next, instead of a OCH2-H···N hydrogen-
bond interaction, the N in the cyano group also interacted
with H in alkene to form CÀH···N interaction with a much
closer distance (2.56 Š). More importantly, an intermolecular
p–p interaction was detected (dp–p =3.38 Š), which tended to
form excimers. Thus, the luminous efficiency was consumed by
densely aggregation.
Figure 5. Molecular orbitals and energy levels of 6b, 6c, and 6e obtained
from DFT calculations [B3LYP/6-31G (d) level] by Gaussian 09 program[13]
The lower and upper orbital diagrams represent HOMO and LUMO, respec-
tively.
.
Conclusions
are 13.18 and 13.48, respectively (q1 =13.18). This non-planar
structure could potentially suppress the intermolecular face-to-
face packing. It was noted that the cyano group could interact
with one of the hydrogen atoms in -OCH3 to form an intermo-
lecular CÀH···N hydrogen bond, and the interaction distances
of two arrangement directions are 2.61 Š and 2.65 Š, respec-
tively (Figure 2d). The twisted molecular plane and supra-
molecular hydrogen-bond interaction led to a cross-like pack-
ing arrangement (Figure 2c), which can effectively minimize
the quenching in fluorescence caused by solid aggregation to
give a 70.2% fluorescence quantum yield in the solid state.
By comparison, compound 6c with a similar structure to its
regioisomer 6b, however, gave only 0.8% fluorescence quan-
tum yield (70.2% for 6b). This regioisomeric effect could be ex-
plained by the over twisted molecular configuration. In the
single crystal structure (Figure 3 and Figure S9 in the Support-
ing Information), two conformations were observed in one
structure that showed an axial chirality relationship, in which
dihedral angles q1 and q2 could be considered as phenyl ring
rotating in a different direction. The whole p system is highly
twisted and the dihedral angle between the phenyl ring and
diene is 388 (q1 and q2), and the dihedral angle between two
phenyl rings is 518. Such a non-planar form intensely paralyzed
the reasonable emission configuration, and this resulted in
weaker fluorescence. Meanwhile, the stronger warping struc-
ture was consistent with HOMO–LUMO gap increasing in pack-
ing state: in diluted solution, 6c gave narrower band gap than
6b (Table 2, 2.94 to 3.05 eV). However, in crystal packing, the
gap value of 6c was slightly larger (Figure 5 and Figure S11 in
the Supporting Information, 3.29 to 3.27 eV). Also, two types
of intermolecular interaction resulted in different packing pat-
terns (Figure 3c): the upper layer was induced by CH···CH inter-
action with distance d1 =2.40 Š; the lower layer was induced
by CÀH···N interaction, which became weaker compared to 6b
(d2 =2.74 Š). The axial chirality was produced in this process.
As expected, with the D–p–A substitution pattern, com-
pound 6e exhibited a much smaller band gap than 6b and 6c
by dramatically lowering the LUMO orbital energy through in-
troducing an electron-withdrawing group (Figure 5, DE=
2.91 eV), by which the emission bands of compound 6e in
In conclusion, three types of substituted a-cyano-a,w-diaryloli-
govinylenes from ethylene to triene were efficiently synthe-
sized through a Knoevenagel condensation reaction. It was
found that the solid-fluorescent emission wavelength could be
tuned by the conjugation length and different substitutent var-
iations. The emission covered the whole visible region with
center wavelength ranging from 412 nm to 684 nm in the
solid state. Notably, the diene moieties showed full-color dis-
plays in powder form by simply introducing donor or acceptor
functional groups and switching their positions. Some struc-
ture–property relationships were rationalized by a combination
of X-ray crystallography and DFT calculations. Comparing to
other full-color display compounds, the advantages of these
structures are their simple preparation and small size, which
would provide more potential for practical applications. Mean-
while, investigations to suppress the densely fluorescence
quenching are in process.
Experimental Section
General Information
All reactions that required anhydrous conditions were carried out
using standard procedures under argon. Commercially available
substrates such as p-substituted 2-phenyl acetonitriles 1a–1 f, p-
substituted aromatic aldehyde 2a–2c, and 3a–3c were used as re-
ceived. The solvents were dried by distillation over the appropriate
drying reagents. The petroleum ether (PE) used had a boiling
range of 60–908C. Reactions were monitored by TLC on silica gel
GF 254 plates. Column chromatography was generally performed
through silica gel (200–300 mesh). Melting points were recorded
with an X-4 microscope melting point apparatus and are uncor-
rected. 1H and 13C NMR spectra were recorded on a Bruker
Avance 400 (400 MHz for 1H and 100 MHz for 13C), as were the
DEPT 135 experiments. Chemical shift values are given in ppm and
1
coupling constants (J) in Hertz. Residual solvent signals in the H
and 13C NMR spectra were used as an internal reference (CDCl3:
dTMS =0, dC =77.0 ppm; [D6]DMSO: dH =2.50, dC =39.5 ppm). Multi-
plicity was indicated as follows: s (singlet), d (doublet), t (triplet), q
(quartet), m (multiplet), dd (doublet of doublet), ddd (doublet of
doublet of doublets). High resolution mass spectra were obtained
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on a Bruker Daltonics APEX III 47e FT-ICR mass spectrometer or on
a Fisons VG Autospec double focusing sector-field instrument by
using electrospray ionization (ESI) techniques. UV/Vis absorptions
were carried out on a UV-Cary100 spectrophotometer. The fluores-
cence spectra and the fluorescence quantum yields were measured
from the solution and powder form using the Edinburgh Instru-
ments (FLS920). Single crystal X-ray diffraction measurements were
performed with a Bruker X8 APEX diffractometer working with
graphite monochromated MoKa and CuKa radiation.
d=8.38 (d, J=8.8 Hz, 2H), 8.12 (d, J=8.8 Hz, 2H), 8.11 (s, 1H), 7.77
(d, J=8.8 Hz, 2H), 7.11 (d, J=8.8 Hz, 2H), 3.84 ppm (s, 3H). The
data were in agreement with the literature.[14]
(Z)-3-(4-Methoxyphenyl)-2-(4-nitrophenyl)acrylonitrile (5 f):
The title compound 5 f was prepared from 1c (648 mg, 4.00 mmol)
and 2b (486 mL, d=1.12 gmLÀ1, 4.00 mmol) as a yellow solid
1
(616 mg, 55%). M.p. 158–1598C; H NMR (400 MHz, CDCl3): d=8.30
(d, J=8.8 Hz, 2H), 7.96 (d, J=8.8 Hz, 2H), 7.82 (d, J=8.8 Hz, 2H),
7.61 (s, 1H), 7.02 (d, J=8.8 Hz, 2H), 3.90 ppm (s, 3H). The data
were in agreement with the literature.[15]
The Preparation and Characterization Data of Compounds
5a–5 f, 6a–6i, and 7a–7 f(Z)-2,3-Diphenylacrylonitrile (5a):
Compounds 6a–6i were synthesized using p-substituted 2-phenyl-
acetonitriles 1a–1 f and aldehydes 3a–3c as substrates according
to the procedure given above for compound 5a [When nitro-sub-
stituted 2-(4-nitrophenyl)acetonitrile (1c) was used, NaOCH3
(0.05 equiv) was required. When the solubility for some substrates
was not good in EtOH, THF was added to increase the solubility.
To a solution of 2-phenylacetonitrile (1a, 462 mL, d=1.02 gmLÀ1
,
4.00 mmol) in EtOH (20 mL) was added benzaldehyde 2a (404 mL,
d=1.05 gmLÀ1, 4.00 mmol) and fresh prepared 1m NaOCH3 solu-
tion in methanol (0.4 mL, 0.40 mmol) with stirring. Then the mix-
ture was stirred at room temperature for around 10 h, and the pre-
cipitate formed. The reaction mixture was placed at 08C for
a while before filtration to afford a white solid. The solid was
washed with cold EtOH to provide the title compound (575 mg,
70%). M.p. 85–868C; 1H NMR (400 MHz, CDCl3): d=7.91–7.89 (m,
2H), 7.70–7.68 (m, 2H), 7.55 (s, 1H), 7.50–7.38 ppm (m, 6H). The
data were in agreement with the literature.[14]
(2Z,4E)-2,5-Diphenylpenta-2,4-dienenitrile (6a):
The title compound 6a was prepared from 1a (462 mL, d=
1.02 gmLÀ1
,
4.00 mmol) and 3a (504 mL, d=1.05 gmLÀ1
,
4.00 mmol) as
a white solid (758 mg, 82%). M.p. 116–1178C;
1H NMR (400 MHz, CDCl3): d=7.63 (d, J=7.6 Hz, 2H), 7.56 (d, J=
7.2 Hz, 2H), 7.45–7.35 (m, 8H), 7.01–6.99 ppm (m, 1H). The data
were in agreement with the literature.[16]
Compounds 5b–5 f were synthesized using p-substituted 2-phenyl
acetonitriles 1a–1c and aldehydes 2a–2c as substrates according
to the procedure given above for compound 5a (When nitro-sub-
stituted 2-(4-nitrophenyl)acetonitrile (1c) was used, NaOCH3
(0.05 equiv) was required). When the solubility for some substrates
was not good in EtOH, THF was added to increase the solubility.
(2Z,4E)-2-(4-Methoxyphenyl)-5-phenylpenta-2,4-dienenitrile
(6b):
The title compound 6b was prepared from 1b (544 mL, d=
(Z)-2-(4-Methoxyphenyl)-3-phenylacrylonitrile (5b):
1.08 gmLÀ1
,
4.00 mmol) and 3a (504 mL, d=1.05 gmLÀ1
,
4.00 mmol) as a green solid (804 mg, 77%). M.p. 159–1608C;
1H NMR (400 MHz, CDCl3): d=7.58–7.53 (m, 4H), 7.40–7.31 (m, 5H),
6.99–6.93 (m, 3H), 3.85 ppm (s, 3H); 13C NMR (100 MHz, CDCl3): d=
160.4 (C), 140.0 (CH), 139.5 (CH), 135.9 (C), 129.3 (CH), 128.9 (CH),
127.4 (CH), 127.0 (CH), 125.8 (C), 125.3 (CH), 117.1 (C), 114.5 (CH),
112.7 (C), 55.4 ppm (CH3); HRMS (ESI): m/z calcd for C18H15NO+H+:
262.1226 [M+H+]; found: 262.1223.
The title compound 5b was prepared from 1b (544 mL, d=
1.08 gmLÀ1
,
4.00 mmol) and 2a (404 mL, d=1.05 gmLÀ1
,
1
4.00 mmol) as a white solid (639 mg, 68%). M.p. 87–888C; H NMR
(400 MHz, CDCl3): d=7.87 (d, J=7.6 Hz, 2H), 7.62 (d, J=8.8 Hz,
2H), 7.48–7.42 (m, 4H), 6.97 (d, J=8.8 Hz, 2H), 3.86 ppm (s, 3H).
The data were in agreement with the literature.[14]
(Z)-2-Phenyl-3-(4-methoxyphenyl)acrylonitrile (5c):
(2Z,4E)-5-(4-Methoxyphenyl)-2-phenylpenta-2,4-dienenitrile
(6c):
The title compound 5c was prepared from 1a (462 mL, d=
1.02 gmLÀ1
,
4.00 mmol) and 2b (486 mL, d=1.12 gmLÀ1
,
1
The title compound 6c was prepared from 1a (347 mL, d=
1.02 gmLÀ1, 3.00 mmol) and 3b (486 mg, 3.00 mmol) as a green
solid (634 mg, 81%). M.p. 136–1378C; 1H NMR (400 MHz, CDCl3):
d=7.63–7.61 (m, 2H), 7.51 (d, J=8.8 Hz, 2H), 7.44–7.39 (m, 3H),
7.35 (d, J=7.2 Hz, 1H) 7.31–7.24 (m, 1H), 6.98 (d, J=11.2 Hz, 1H),
6.92 (d, J=8.8 Hz, 2H), 3.85 ppm (s, 3H); 13C NMR (100 MHz,
CDCl3): d=160.9 (C), 142.1 (CH), 141.0 (CH), 133.5 (C), 129.1 (CH),
129.0 (CH), 128.8 (CH), 128.6 (C), 125.5 (CH), 123.2 (CH), 117.3 (C),
114.5 (CH), 111.6 (C), 55.4 ppm (CH3). The data were in agreement
with the literature.[16]
4.00 mmol) as a white solid (677 mg, 72%). M.p. 88–898C; H NMR
(400 MHz, CDCl3): d=7.89 (d, J=8.8 Hz, 2H), 7.66 (d, J=8.8 Hz,
2H), 7.47–7.35 (m, 4H), 6.98 (d, J=8.8 Hz, 2H), 3.87 ppm (s, 3H).
The data were in agreement with the literature.[14]
(Z)-2,3-Bis(4-methoxyphenyl)acrylonitrile (5d):
The title compound 5d was prepared from 1b (544 mL, d=
1.08 gmLÀ1
,
4.00 mmol) and 2b (486 mL, d=1.12 gmLÀ1
,
4.00 mmol) as a light green solid (700 mg, 66%). M.p. 102–1038C;
1H NMR (400 MHz, CDCl3): d=7.85 (d, J=8.8 Hz, 2H), 7.58 (d, J=
8.8 Hz, 2H), 7.36 (s, 1H), 6.97 (d, J=8.8 Hz, 2H), 6.95 (d, J=8.8 Hz,
2H), 3.87 (s, 3H), 3.85 ppm (s, 3H). The data were in agreement
with the literature.[14]
(2Z,4E)-2,5-Bis(4-methoxyphenyl)penta-2,4-dienenitrile (6d):
The title compound 6d was prepared from 1b (408 mL, d=
1.08 gmLÀ1, 3.00 mmol) and 3b (486 mg, 3.00 mmol) as a green
solid (742 mg, 85%). M.p. 161–1628C; 1H NMR (400 MHz, CDCl3):
d=7.53 (d, J=8.8 Hz, 2H), 7.48 (d, J=8.8 Hz, 2H), 7.29–7.20 (m,
2H), 6.95–6.90 (m, 5H), 3.84 (s, 3H), 3.84 ppm (s, 3H); 13C NMR
(100 MHz, CDCl3): d=160.6 (C), 160.2 (C), 140.0 (CH), 139.8 (CH),
128.9 (CH), 128.8 (C), 126.8 (CH), 126.1 (C), 123.3 (CH), 117.4 (C),
(Z)-2-(4-Methoxyphenyl)-3-(4-nitrophenyl)acrylonitrile (5e):
The title compound 5e was prepared from 1b (408 mL, d=
1.08 gmLÀ1, 3.00 mmol) and 2c (453 mg, 3.00 mmol) as an orange
1
solid (403 mg, 48%). M.p. 94–968C; H NMR (400 MHz, [D6]DMSO):
Chem. Asian J. 2015, 10, 1959 – 1966
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114.4 (CH), 114.3 (CH), 111.3 (C), 55.4 (CH3), 55.3 ppm (CH3); HRMS
(ESI): m/z calcd for C19H17NO2+H+: 292.1332 [M+H+]; found:
292.1328.
129.4 (CH), 129.2 (CH), 128.9 (CH), 127.3 (CH), 126.43 (CH), 126.37
(C), 125.4 (CH), 125.0 (CH), 123.8 (CH), 122.4 (CH), 117.1 (C),
112.8 ppm (C); HRMS (ESI): m/z calcd for C29H22N2+H+: 399.1856
[M+H+]; found: 399.1851.
Compounds 7a–7 f were synthesized using p-substituted 2-phenyl
acetonitriles 1a–1c and aldehydes 4a–4c as substrates according
to the procedure given above for compound 5a (When nitro-sub-
stituted 2-(4-nitrophenyl)acetonitrile (1c) was used, NaOCH3
(0.05 equiv) was required. When the solubility for some substrates
was not good in EtOH, THF was added to increase the solubility.
(2Z,4E)-2-(4-Methoxyphenyl)-5-(4-nitrophenyl)penta-2,4-di-
enenitrile (6e):
The title compound 6e was prepared from 1b (408 mL, d=
1.08 gmLÀ1, 3.00 mmol) and 3c (531 mg, 3.00 mmol) as an orange
red solid (716 mg, 78%). M.p. 166–1678C; 1H NMR (400 MHz,
CDCl3): d=8.21 (d, J=8.8 Hz, 2H), 7.64 (d, J=8.8 Hz, 2H), 7.57 (d,
J=8.8 Hz, 2H), 7.53–7.43 (m, 1H), 7.31–7.27 (m, 1H), 7.00–6.93 (m,
3H), 3.85 ppm (s, 3H); 13C NMR (100 MHz, CDCl3): d=161.0 (C),
147.6 (C), 142.2 (C), 137.7 (CH), 136.6 (CH), 129.3 (CH), 127.7 (CH),
127.3 (CH), 125.2 (C), 124.2 (CH), 116.7 (C), 115.8 (C), 114.6 (CH),
55.5 ppm (CH3); HRMS (ESI): m/z calcd for C18H14N2O3+H+:
307.1077 [M+H+]; found: 307.1075.
(2Z,4E,6E)-2,7-Diphenylhepta-2,4,6-trienenitrile (7a):
The title compound 7a was prepared from 1a (176 mL, d=
1.02 gmLÀ1, 1.53 mmol) and 4a (158 mg, 1.00 mmol) as a green
solid (185 mg, 72%). M.p. 136–1378C; 1H NMR (400 MHz, CDCl3):
d=7.62 (d, J=7.2 Hz, 2H), 7.60–7.26 (m, 9H), 7.04–6.97 (m, 2H),
6.94–6.78 ppm (m, 2H); 13C NMR (100 MHz, CDCl3): d=141.5 (CH),
141.2 (CH), 137.7 (CH), 136.4 (C), 133.3 (C), 129.2 (CH), 129.0 (CH),
129.0 (CH), 128.8 (CH), 128.7 (CH), 128.0 (CH), 127.0 (CH), 125.5
(CH), 117.0 (C), 112.5 ppm (C); HRMS (ESI): m/z calcd for
C19H15N+H+: 258.1277 [M+H+]; found: 258.1278.
(2Z,4E)-5-(4-Methoxyphenyl)-2-(4-nitrophenyl)penta-2,4-di-
enenitrile (6 f):
The title compound 6 f was prepared from 1c (486 mg, 3.00 mmol)
and 3b (486 mg, 3.00 mmol) as a red solid (753 mg, 82%).
M.p. 152–1548C; 1H NMR (400 MHz, CDCl3): d=8.28 (d, J=8.8 Hz,
2H), 7.77 (d, J=9.2 Hz, 2H), 7.56 (d, J=11.2 Hz, 1H), 7.55 (d, J=
8.8 Hz, 2H), 7.32 (d, J=11.2 Hz, 1H), 7.12 (d, J=13.2 Hz, 1H), 6.95
(d, J=8.8 Hz, 2H), 3.87 ppm (s, 3H); 13C NMR (100 MHz, CDCl3): d=
161.5 (C), 147.2 (C), 145.5 (CH), 144.3 (CH), 139.6 (C), 129.5 (CH),
128.0 (C), 125.8 (CH), 124.3 (CH), 122.4 (CH), 116.4 (C), 114.5 (CH),
109.0 (C), 55.4 ppm (CH3). The data were in agreement with the lit-
erature.[16]
(2Z,4E,6E)-2-(4-Methoxyphenyl)-7-phenylhepta-2,4,6-triene-
nitrile (7b):
The title compound 7b was prepared from 1b (117 mL, d=
1.08 gmLÀ1, 0.86 mmol) and 4a (136 mg, 0.86 mmol) as a green
solid (188 mg, 76%). M.p. 153–1548C; 1H NMR (400 MHz, CDCl3):
d=7.55 (d, J=8.8 Hz, 2H), 7.46 (d, J=7.2 Hz, 2H), 7.38–7.34 (m,
2H), 7.29 (d, J=7.2 Hz, 1H), 7.22 (d, J=11.2 Hz, 1H), 7.03–6.91 (m,
4H), 6.83–6.75 (m, 2H), 3.85 ppm (s, 3H); 13C NMR (100 MHz,
CDCl3): d=160.3 (C), 140.3 (CH), 139.1 (CH), 137.0 (CH), 136.5 (C),
129.4 (CH), 128.8 (CH), 128.5 (CH), 128.2 (CH), 126.9 (CH), 126.8
(CH), 125.9 (C), 117.2 (C), 114.4 (CH), 112.1 (C), 55.4 ppm (CH3);
HRMS (ESI): m/z calcd for C20H17NO+H+: 288.1383 [M+H+]; found:
288.1383.
(2Z,4E)-2-[4-(Diethylamino)phenyl]-5-phenylpenta-2,4-diene-
nitrile (6g):
The title compound 6g was prepared from 1d (131 mg,
0.70 mmol) and 3a (88 mL, d=1.05 gmLÀ1, 0.70 mmol) as a yellow
solid (154 mg, 73%). M.p. 106–1078C; 1H NMR (400 MHz, CDCl3):
d=7.53–7.47 (m, 4H), 7.40–7.27 (m, 4H), 7.19 (d, J=11.2 Hz, 1H),
6.88 (d, J=15.6 Hz, 1H), 6.66 (d, J=8.8 Hz, 2H), 3.39 (q, J=7.2 Hz,
4H), 1.19 ppm (t, J=7.2 Hz, 6H); 13C NMR (100 MHz, CDCl3): d=
148.2 (C), 137.8 (CH), 136.4 (C), 136.0 (CH), 128.8 (CH), 128.7 (CH),
127.1 (CH), 126.9 (CH), 125.8 (CH), 120.0 (C), 117.4 (C), 113.4 (C),
111.5 (CH), 44.4 (CH2), 12.6 ppm (CH3); HRMS (ESI): m/z calcd for
C21H22N2+H+: 303.1856 [M+H+]; found: 303.1850.
(2Z,4E,6E)-7-(4-Methoxyphenyl)-2-phenylhepta-2,4,6-triene-
nitrile (7c):
The title compound 7c was prepared from 1a (102 mL, d=
1.02 gmLÀ1, 0.88 mmol) and 4b (113 mg, 0.60 mmol) as green solid
1
(121 mg, 70%). M.p. 145–1468C; H NMR (400 MHz, CDCl3): d=7.60
(d, J=7.6 Hz, 2H), 7.43–7.39 (m, 4H), 7.36–7.32 (m, 2H), 6.95–6.73
(m, 6H), 3.84 ppm (s, 3H); 13C NMR (100 MHz, CDCl3): d=160.2 (C),
142.0 (CH), 141.5 (CH), 137.5 (CH), 133.4 (C), 129.3 (C), 129.0 (CH),
128.8 (CH), 128.4 (CH), 128.2 (CH), 126.0 (CH), 125.5 (CH), 117.2 (C),
114.4 (CH), 111.7 (C), 55.3 ppm (CH3); HRMS (ESI): m/z calcd for
C20H17NO+H+: 288.1383 [M+H+]; found: 288.1382.
(2Z,4E)-5-Phenyl-2-(p-tolyl)penta-2,4-dienenitrile (6h)
The title compound 6h was prepared from 1e (527 mL, d=
0.994 gmLÀ1
,
4.00 mmol) and 3a (504 mL, d=1.05 gmLÀ1
,
4.00 mmol) as a yellow solid (666 mg, 68%). M.p. 136–1388C;
1H NMR (400 MHz, CDCl3): d=7.56–7.50 (m, 4H), 7.42–7.30 (m, 5H),
7.22 (d, J=8.0 Hz, 2H), 7.03–6.94 (m, 1H), 2.38 ppm (s, 3H). The
data were in agreement with the literature.[17]
(2Z,4E,6E)-2,7-Bis(4-methoxyphenyl)hepta-2,4,6-trienenitrile
(7d):
The title compound 7d was prepared from 1b (120 mL, d=
1.08 gmLÀ1, 0.88 mmol) and 4b (113 mg, 0.60 mmol) as a green
solid (133 mg, 70%). M.p. 143–1448C; 1H NMR (400 MHz, CDCl3):
d=7.53 (d, J=8.8 Hz, 2H), 7.40 (d, J=8.8 Hz, 2H), 7.21 (d, J=
11.2 Hz, 1H), 6.94–6.86 (m, 6H), 6.83–6.70 (m, 2H), 3.84 (s, 3H),
3.83 ppm (s, 3H); 13C NMR (100 MHz, CDCl3): d=160.1 (C), 160.0
(C), 140.8 (CH), 139.5 (CH), 136.8 (CH), 129.4 (C), 128.4 (CH), 128.3
(CH), 126.8 (CH), 126.2 (CH), 126.0 (C), 117.3 (C), 114.4 (CH), 114.3
(CH), 111.3 (C), 55.4 (CH3), 55.3 ppm (CH3); HRMS (ESI): m/z calcd
for C21H19NO2+H+: 318.1489 [M+H+]; found: 318.1488.
(2Z,4E)-2-(4-(Diphenylamino)phenyl)-5-phenylpenta-2,4-dien-
enitrile (6i)
The title compound 6i was prepared from 1 f (284 mg, 1.00 mmol)
and 3a (126 mL, d=1.05 gmLÀ1, 1.00 mmol) as a yellow solid
1
(263 mg, 66%). M.p. 155–1568C; H NMR (400 MHz, CDCl3): d=7.53
(d, J=7.2 Hz, 2H), 7.46 (d, J=8.8 Hz, 2H), 7.42–7.23 (m, 9H), 7.15–
7.02 (m, 8H), 6.95 ppm (d, J=15.2 Hz, 1H); 13C NMR (100 MHz,
CDCl3): d=148.7 (C), 147.0 (C), 139.8 (CH), 139.1 (CH), 136.0 (C),
Chem. Asian J. 2015, 10, 1959 – 1966
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1964
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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8.8 Hz, 2H), 7.60 (d, J=8.8 Hz, 2H), 7.44 (dd, J=15.6, 10.4 Hz, 1H),
7.05–6.91 (m, 2H), 6.11 (d, J=15.6 Hz, 1H), 4.25 (q, J=7.2 Hz, 2H),
1.33 ppm (t, J=7.2 Hz, 3H). The data were in agreement with the
literature.[20]
(2Z,4E,6E)-2-(4-Methoxyphenyl)-7-(4-nitrophenyl)hepta-2,4,6-
trienenitrile (7e):
The title compound 7e was prepared from 1b (145 mL, d=
1.08 gmLÀ1, 1.07 mmol) and 4c (180 mg, 0.89 mmol) as a red solid
1
(180 mg, 61%). M.p. 201–2038C; H NMR (400 MHz, CDCl3): d=8.22
(d, J=8.8 Hz, 2H), 7.67–7.51 (m, 4H), 7.24 (d, J=11.6 Hz, 1H), 7.16–
7.02 (m, 2H), 6.95 (d, J=8.8 Hz, 2H), 6.83–6.77 (m, 2H), 3.86 ppm
(s, 3H); 13C NMR (100 MHz, CDCl3): d=160.7 (C), 147.1 (C), 143.0
(C), 138.7 (CH), 138.1 (CH), 133.8 (CH), 132.5 (CH), 132.2 (CH), 127.2
(CH), 125.6 (C), 124.2 (CH), 116.8 (C), 114.6 (CH), 114.3 (C), 55.5 ppm
(CH3), one overlapping Ar-CH resonance; HRMS (ESI): m/z calcd for
C20H16N2O3+H+: 333.1234 [M+H+]; found: 333.1234.
(2E,4E)-5-Phenylpenta-2,4-dien-1-ol (9a):
Compound 9a was synthesized from 8a according to a literature
procedure.[18] DIBAL-H (5.17 mL, 1.5m in toluene) was added to
a solution of 8a (525 mg, 2.60 mmol) in CH2Cl2 (20 mL), the mix-
ture was stirred at room temperature until no starting material re-
mained (TLC plate checking). Then saturated potassium sodium
tartrate tetrahydrate solution (20 mL) was added to the reaction
mixture until the reaction mixture became clear. The resulting mix-
ture was extracted with CH2Cl2 (20 mL) and EtOAc (20 mL”2). The
organic layer was separated, dried with anhydrous MgSO4, and
concentrated in vacuum. The residue was purified by silica gel
flash chromatography to give the title compound as a white solid
(379 mg, 91%). Rf =0.47 (petroleum ether/ethyl acetate 2:1);
1H NMR (400 MHz, CDCl3): d=7.39 (d, J=7.4 Hz, 2H), 7.31 (t, J=
7.4 Hz, 2H), 7.22 (t, J=7.4 Hz, 1H), 6.78 (dd, J=15.6, 10.5 Hz, 1H),
6.55 (d, J=15.6 Hz, 1H), 6.41 (dd, J=15.1, 10.5 Hz, 1H), 5.99–5.91
(m, 1H), 4.23 (d, J=5.7 Hz, 2H), 1.71 ppm (br, 1H). The data were
identical with those in the reference.[18]
(2Z,4E,6E)-7-(4-Methoxyphenyl)-2-(4-nitrophenyl)hepta-2,4,6-
trienenitrile (7 f):
The title compound 7 f was prepared from 1c (86 mg, 0.53 mmol)
and 4b (100 mg, 0.53 mmol) as a dark red solid (114 mg, 65%).
M.p. 195–1968C; 1H NMR (400 MHz, CDCl3): d=8.27 (d, J=9.2 Hz,
2H), 7.75 (d, J=9.2 Hz, 2H), 7.52–7.48 (m, 1H), 7.44 (d, J=8.8 Hz,
2H), 7.00–6.82 (m, 6H), 3.85 ppm (s, 3H); 13C NMR (100 MHz,
CDCl3): d=160.6 (C), 147.3 (C), 145.2 (CH), 144.8 (C), 139.8 (CH),
139.7 (C), 128.9 (CH), 128.8 (CH), 127.5 (CH), 125.9 (CH), 125.6 (CH),
124.3 (CH), 116.3 (C), 114.4 (CH), 109.0 (C), 55.4 ppm (CH3); HRMS
(ESI): m/z calcd for C20H16N2O3+H+: 333.1234 [M+H+]; found:
333.1234.
Compounds 9b and 9c were synthesized using 8b and 8c as sub-
strates according to the procedure given above for compound 9a.
(2E,4E)-Ethyl-5-phenylpenta-2,4-dienoate (8a):
(2E,4E)-5-(4-Methoxyphenyl)penta-2,4-dien-1-ol (9b):
Compound 8a was synthesized from 3a according to a literature
procedure.[18] To a solution of (2-ethoxy-2-oxoethyl) triphenylphos-
phonium salt (2.57 g, 6.00 mmol) in THF (30 mL) was added NaOH
(240 mg, 6.00 mmol) with some drops of water. The mixture was
stirred at room temperature for 10 min, then cinnamaldehyde (3a,
660 mg, 5.00 mmol) was added to the above reaction mixture. The
reaction system became clear and stirred until no aldehyde re-
mained. The solvent was removed under vacuum. The residue was
purified by silica-gel flash chromatography to give the title com-
pound as a colorless liquid (778 mg, 77%). Rf =0.58 (petroleum
ether/ethyl acetate 5:1); 1H NMR (400 MHz, CDCl3): d=7.48–7.41
(m, 3H), 7.38–7.28 (m, 3H), 6.93–6.83 (m, 2H), 5.99 (d, J=15.3 Hz,
1H), 4.23 (q, J=7.2 Hz, 2H), 1.32 ppm (t, J=7.2 Hz, 3H). The data
were in agreement with the literature.[18]
The title compound 9b was prepared from 8b (603 mg,
2.60 mmol) and DIBAL-H (5.17 mL, 1.5m in toluene) as white solid
(445 mg, 90%). Rf =0.39 (petroleum ether/ethyl acetate 2:1);
1H NMR (400 MHz, CDCl3): d=7.36 (d, J=8.8 Hz, 2H), 6.85 (d, J=
8.8 Hz, 2H), 6.67 (dd, J=15.6, 10.4 Hz, 1H), 6.51 (d, J=15.6 Hz, 1H),
6.40 (dd, J=15.2, 10.4 Hz, 1H), 5.95–5.88 (m, 1H), 4.24 (d, J=
6.0 Hz, 2H), 3.81 ppm (s, 3H). The data were in agreement with the
literature.[21]
(2E,4E)-5-(4-Nitrophenyl)penta-2,4-dien-1-ol (9c):
The title compound 9c was prepared from 8c (642 mg, 2.60 mmol)
and DIBAL-H (5.17 mL, 1.5m in toluene) as a white solid (469 mg,
88%). Rf =0.45 (petroleum ether/ethyl acetate 2:1); 1H NMR
(400 MHz, CDCl3): d=8.18 (d, J=8.8 Hz, 2H), 7.52 (d, J=8.8 Hz,
2H), 6.94 (dd, J=15.6, 11.8 Hz, 1H), 6.60 (d, J=15.6 Hz, 1H), 6.48
(dd, J=15.2, 11.8 Hz, 1H), 6.14–6.08 (m, 1H), 4.31 ppm (d, J=
4.4 Hz, 2H). The data were in agreement with the literature.[20]
Compounds 8b and 8c were synthesized using 3b and 3c as sub-
strates, respectively, according to the procedure given above for
compound 8a.
(2E,4E)-Ethyl-5-(4-methoxyphenyl)penta-2,4-dienoate (8b):
The title compound 8b was prepared from 3b (810 mg,
5.00 mmol) and (2-ethoxy-2-oxoethyl)triphenylphosphonium salt
(2.57 g, 6.00 mmol) as white solid (870 mg, 75%). Rf =0.52 (petrole-
um ether/ethyl acetate 5:1); 1H NMR (400 MHz, CDCl3): d=7.47–
7.40 (m, 3H), 6.91–6.88 (m, 3H), 6.78–6.72 (q, 1H), 5.94 (d, J=
15.6 Hz, 1H), 4.22 (q, J=7.2 Hz, 2H), 3.83 (s, 3H), 1.31 ppm (t, J=
7.2 Hz, 3H). The data were in agreement with the literature.[19]
(2E,4E)-5-Phenylpenta-2,4-dienal (4a):
Compound 4a was synthesized from 9a by following a literature
procedure.[18] Dess–Martin periodinane (933 mg, 2.20 mmol) was
added to a solution of 9a (288 mg, 1.80 mmol) in CH2Cl2 (20 mL)
and the mixture was stirred at room temperature until no starting
material remained (TLC plate checking). The solvent was removed
under vacuum. The residue was purified by silica-gel flash chroma-
tography to give the title compound as a light yellow liquid
(213 mg, 75%). Rf =0.76 (petroleum ether/ethyl acetate 2:1);
1H NMR (400 MHz, CDCl3): d=9.62 (d, J=8.0 Hz, 1H), 7.53–7.49 (m,
2H), 7.41–7.35 (m, 3H), 7.27 (ddd, J=15.2, 7.2, 3.0 Hz, 1H), 7.02–
7.00 (m, 2H), 6.28 ppm (dd, J=15.2, 8.0 Hz, 1H). The data were in
agreement with the literature.[18]
(2E,4E)-Ethyl-5-(4-nitrophenyl)penta-2,4-dienoate (8c):
The title compound 8c was prepared from 3c (885 mg, 5.00 mmol)
and (2-ethoxy-2-oxoethyl)triphenylphosphonium salt (2.57 g,
6.00 mmol) as a white solid (889 mg, 72%). Rf =0.75 (petroleum
1
ether/ethyl acetate 5:1); H NMR (400 MHz, CDCl3): d=8.22 (d, J=
Chem. Asian J. 2015, 10, 1959 – 1966
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1965
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
K. An, S.-K. Kwon, S.-D. Jung, S. Y. Park, J. Am. Chem. Soc. 2002, 124,
14410–14415; c) A. Qin, B. Z. Tang, Aggregation-Induced Emission: Fun-
damentals and Applications, Wiley-VCH, Weinheim, 2013, pp. 2–167.
[7] a) Z. Ning, Z. Chen, Q. Zhang, Y. Yan, S. Qian, Y. Cao, H. Tian, Adv. Funct.
Mater. 2007, 17, 3799–3807; b) Y. Hong, J. W. Y. Lam, B. Z. Tang, Chem.
Commun. 2009, 4332–4353; c) Z. Zhao, Z. Wang, P. Lu, C. Y. K. Chan, D.
Liu, J. W. Y. Lam, H. H. Y. Sung, I. D. Williams, Y. Ma, B. Z. Tang, Angew.
Chem. Int. Ed. 2009, 48, 7608–7611; Angew. Chem. 2009, 121, 7744–
7747; d) P. An, Z.-F. Shi, W. Dou, X.-P. Cao, H.-L. Zhang, Org. Lett. 2010,
12, 4364–4367; e) B. Wang, Y. Wang, J. Hua, Y. Jiang, J. Huang, S. Qian,
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4273–4276; Angew. Chem. 2007, 119, 4351–4354; b) M. Shimizu, Y.
Takeda, M. Higashi, T. Hiyama, Angew. Chem. Int. Ed. 2009, 48, 3653–
3656; Angew. Chem. 2009, 121, 3707–3710; c) Z. Zhang, B. Xu, J. Su, L.
Shen, Y. Xie, H. Tian, Angew. Chem. Int. Ed. 2011, 50, 11654–11657;
Angew. Chem. 2011, 123, 11858–11861; d) D. Zhao, G. Li, D. Wu, X. Qin,
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13925.
Compounds 4b and 4c were synthesized using 9b and 9c as sub-
strates, respectively, according to the procedure given above for
compound 4a.
(2E,4E)-5-(4-Methoxyphenyl)penta-2,4-dienal (4b):
The title compound 4b was prepared from 9b (342 mg,
1.80 mmol) and Dess–Martin periodinane (933 mg, 2.20 mmol) as
white solid (247 mg, 73%). Rf =0.62 (petroleum ether/ethyl acetate
2:1); 1H NMR (400 MHz, CDCl3): d=9.60 (d, J=8.0 Hz, 1H), 7.48–
7.44 (m, 2H), 7.25 (dd, J=15.2, 10.4 Hz, 1H), 7.00–6.85 (m, 4H),
6.23 (dd, J=14.8, 8.0 Hz, 1H), 3.85 ppm (s, 3H). The data were in
agreement with the literature.[22]
(2E,4E)-5-(4-Nitrophenyl)penta-2,4-dienal (4c):
The title compound 4c was prepared from 9c (369 mg, 1.80 mmol)
and Dess–Martin periodinane (933 mg, 2.20 mmol) as white solid
(300 mg, 82%). Rf =0.71 (petroleum ether/ethyl acetate 2:1);
1H NMR (400 MHz, CDCl3): d=9.68 (d, J=8.0 Hz, 1H), 8.25–8.23 (d,
J=8.8 Hz, 2H), 7.65 (d, J=8.8 Hz, 2H), 7.32–7.25 (m, 1H), 7.17–7.04
(m, 2H), 6.36 ppm (dd, J=8.0, 7.2 Hz, 1H). The data were in agree-
ment with the literature.[23]
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The authors are grateful to the National Natural Science Foun-
dation of China (Grant Nos. 21272098 and 21190034), the Pro-
gram for Changjiang Scholars and Innovative Research Team in
University (PCSIRT: IRT1138), the Fundamental Research Funds
for the Central University (FRFCU: lzujbky-2013-ct02), and the
111 Project for financial support. We gratefully acknowledge
professor Hak-Fun Chow in the Chinese University of Hong
Kong for his helpful guidance in the preparation of the manu-
script and Yong-Liang Shao in Lanzhou University for X-ray
crystallographic analyses.
Keywords: dyes/pigments
· fluorescence · single crystal
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Manuscript received: May 7, 2015
Accepted Article published: July 7, 2015
Final Article published: August 6, 2015
Chem. Asian J. 2015, 10, 1959 – 1966
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