The configuration, solvatochromism and metallo-responses of two novel cyano-containing oligo(phenylene-vinylene) derivatives

Article abstract of DOI:10.1002/bio.1204

Two novel cyano-containing oligo(phenylenevinylene) (OPV) derivatives have been designed and synthesized. Photophysical and sensing properties of the two compounds were studied. Such studies reveal the intramolecular charge transfer process between cyano

Full text of DOI:10.1002/bio.1204

Research article
Received: 13 October 2009,
Revised: 18 December 2009,
Accepted: 14 January 2010,
Published online in Wiley Online Library: 22 March 2010
(wileyonlinelibrary.com) DOI 10.1002/bio.1204
The configuration, solvatochromism
and metallo-responses of two novel
cyano-containing oligo(phenylene-vinylene)
derivatives
Jing Lv,ab Xiaodong Yin,ab Haiyan Zheng,ab Yongjun Li,a Yuliang Li*a and
Daoben Zhua
ABSTRACT: Two novel cyano-containing oligo(phenylenevinylene) (OPV) derivatives have been designed and synthesized.
Photophysical and sensing properties of the two compounds were studied. Such studies reveal the intramolecular charge
transfer process between cyano groups and OPV core. The results showed that the alkyl difference of substituted OPV leads to
the changes of molecular configuration and metallo-response of two compounds. Copyright © 2010 John Wiley & Sons, Ltd.
Keywords: cyano; charge transfer; twisted configuration; solvatochromism; sensor
Introduction
Experimental
p-Conjugated organic materials with donors and acceptors have
unique optical and electronical properties (1–3). In the past
decades, many molecules containing di- and tri-chromophoric
units have been investigated in order to control the the process
of charge transfer (4,5). These molecular systems have aroused
great interest owing to their considerable potential application
in field, such as organic light emitting diodes (OLED) (6,7), field-
effect transitors (FETs) (8,9), nonlinear optical devices (10,11),
solar cells (12,13) and chemical sensors (14–18). The oligo(phe-
nylenevinylene) (OPV)-based materials have received a great
deal of attention, due to their specific photophysical properties
and high quantum yields (19,20). Conjugated linkage of
cyano groups to the OPV core could increase electron delocal-
ization and lead to intramolecular charge transfer (ICT) effect in
the molecular systems, resulting in unique photophysical
properties. However, the fine tuning of OPV molecular struc-
ture for producing new properties has not been well
studied.
Novel acceptor–p–acceptor systems were designed and the
goal was to disclose the different performances of the these
systems due to their different substituted groups. We describe
herein the synthesis, configuration, photophysics and metallo-
responses of the cyano-containing OPV systems. The configura-
tion, photophysical and sensing properties of the alkyl
substituted OPV compounds were compared, and the results
showed that the molecular configuration and metallo-response
depend on the different alkyl chains on the OPV core. 2,2′-{4,4′-
(1E,1′E)-2,2′-[2,5-bis(dodecyloxy)-1,4-phenylene] bis(ethene-2,1-
diyl)bis (4,1-phenylene) bis(methan-1-yl-1-ylidene) dimalononi-
trile} (OPVCN4–C12) was proved to be a good dual-modal
colorimetric and fluorometric sensing material for Cu2+
ions.
Reagents were purchased and utilized as received unless indi-
cated otherwise. All solvents were purified using standard proce-
dures. Evaporation and concentration in vacuo were carried out
at water aspirator pressure. Column chromatography used SiO2
(200–300 meshes). UV–vis spectra were measured on a Jasco
V-570 UV–vis–NIR spectrophotometer. The fluorescence spectra
were measured on a Jasco FP-6600 spectro fluorometer. The
400 MHz 1HNMR spectra were recorded on a Bruker Avance DPS-
400 (400 MHz) and a DPS-600 (600 MHz) spectrometer. MALDI-
TOF mass spectrometric measurements were performed on a
Bruker Biflex MALDITOF spectrometer. Elemental analyses were
carried out on a Carlo Erba 1106 elemental analyzer.The synthetic
procedures of OPVCN–C12 and OPVCN–Me are shown in
Scheme 1.
Synthesis of OPVCN4–C12
To a solution of malononitrile (66 mg, 1 mmol) in 2 mL dry dichlo-
romethane was added 800 mg Al2O3. After removing the solvent,
* Correspondence to:Yuliang Li, CAS Key Laboratory of Organic Solids, Beijing
National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry
Chinese Academy of Sciences, Beijing 100190, People’s Republic of China.
E-mail: ylli@iccas.ac.cn
a
CAS Key Laboratory of Organic Solids, Beijing National Laboratory for
Molecular Sciences (BNLMS), Institute of Chemistry Chinese Academy of
Sciences, Beijing 100190, People’s Republic of China
b
Graduate School of Chinese Academy of Sciences, Chinese Academy of Sci-
ences, Beijing, 100190, People’s Republic of China
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J. Lv et al.
Scheme 1. Synthetic route of OPVCN–C12 and OPVCN–Me.
Figure 1. The molecular structures of OPVCN–Me (A) and OPVCN–C12 (B).The optimized configurations of OPVCN–Me (C)
and OPVCN–C12 (D). HOMO orbital (E) and LUMO orbital (F) of OPVCN–Me obtained by DFT calculations.
4,4′-(1E,1′E)-2,2′-(2,5-didodecyloxy-1,4-phenylene)bis(ethene-2,
1-diyl)dibenzaldehyde (50 mg, 0.07 mmol) in 2 mL dry dichlo-
romethane was added to the powder. Then solvent was evapo-
rated and the reactant mixture was kept at room temperature for
8 h. The reaction was monitored by thin-layer chromatography.
Purification of the crude product by column chromatography
(petroleum–chloroform, 1:4), yielded pure product (39 mg, 69%)
as dark red solid. 1H NMR (CDCl3, d, ppm): 7.92 (d, 4H), 7.70 (m, 8H),
7.21 (s, 1H), 7.16 (s, 1H), 7.12 (s, 2H), 4.10 (t, 4H), 1.94 (m, 4H), 1.58
(m, 4H), 1.42 (m, 4H), 1.31–1.25 (m, 32H), 0.89 (t, 6H). 13C NMR
(CDCl3, d, ppm): 158.8, 151.6, 144.4, 131.5, 129.8, 128, 127.5, 127.3
127, 114.2, 113.1, 110.7, 80.9, 69.4, 53.5, 31.9, 29.7, 29.5, 29.4, 26.3,
22.7, 14.2. MS (MALDI-TOF): M = 803.13, 802.8. Anal. calcd for
C54H66N4O2: C, 80.76; H, 8.08; N, 6.98. Found: C, 80.24; H, 8.00; N,
6.90.
dibenzaldehyde (50 mg, 0.1 mmol), malononitrile (66 mg,
1 mmol) and Al2O3 (800 mg). Solid 13CNMR (d, ppm) (1–3): 162.39,
161.69, 153.19, 151.92, 149.60, 147.86, 138.03, 130.91, 129.90,
128.09, 127.34, 124.96, 119.59, 117.60, 109.13, 108.46, 76.83,
75.22, 57.78, 56.30, 34.74. Solid 1H NMR (d, ppm): 9.19, 3.52 (d). MS
(EI): M = 494, 494. Anal. calcd for C32H22N4O2: C, 77.72; H, 4.48; N,
11.32. Found: C, 77.52; H, 4.62; N, 11.08.
The salts of Ca(ClO4)2, Ni(ClO4)2, Co(ClO4)3, Zn(ClO4)2, Cd(ClO4)2,
Pb(ClO4)2, Cu(ClO4)2, Hg(ClO4)2, Fe(ClO4)3 and AgNO3 were dis-
solved in acetonitrile and used for studying metallo-response
experiments.
Results and discussion
Configuration study
OPVCN–Me and OPVCN–C12 were synthesized according to the
solid reaction using Al2O3 as catalyst and carrier, which provides a
simple but efficient way to afford a high yield. The molecular
stuctures of OPVCN–Me and OPVCN–C12 are shown in Fig. 1(A,
B). The structural differences between OPVCN–Me and OPVCN–
C12 lie in the different alkyl chains substituted on the OPV core.
The different alkyl chain of the substituted OPV might lead to
different configurations of two compounds. Density functional
theory (DFT) calculations were performed (21) to optimize con-
Synthesis of 2,2Ј-{4,4Ј-(1E,1ЈE)2,2Ј-[2,5-bis(methyloxy)
1,4-phenylene]bis(ethene-2,1-diyl)bis
(4,1-phenylene)bis(methan-1-yl-1-ylidene)
dimalononitrile} (OPVCN–Me)
The synthesis of OPVCN–Me was performed under a similar
procedure to OPVCN–C12. The start materials were 4,4′-
(1E,1′E)-2,2′-(2,5-dimethyloxy-1,4-phenylene)bis(ethene-2,1-diyl)
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Two novel cyano-containing oligo(phenylene-vinylene) derivatives
Figure 2. The absorption spectra and fluorescence emission spectra of OPVCN–Me (A) and OPVCN–C12 (B) in different solvents
at the concentration of 1 ¥ 10-5 M.
figuration of OPVCN–Me and OPVCN–C12. As the calculation
results showed, both the compounds have non-planar conforma-
tion. The OPVCN–Me molecule slightly twists, resulting in a
helical configuration, whereas the OPVCN–C12 molecule exhibits
symmetric configuration, the middle phenyl of which deviates
from the plane formed by the phenyls and cyano groups on
either side (as shown in Fig. 1C, D).
Solid 13C NMR measurements were performed; the chemical
shifts are sensitive to the subtle differences in the molecular con-
figuration. In the solid 13C NMR spectrum, the peaks at 57.78 and
56.30 ppm were attributed to –OCH3, peaks at 76.83 and 75.22
ppm were assigned to C=C*(CN)2, peaks at 109.13 and 108.46
ppm were ascribed to CN, and peaks at 162.39 and 161.69 ppm
were attributed to C*=C(CN)2. The selected area electron diffrac-
tion (SAED) experiments proved that OPVCN–Me is non-
crystalline, so the resonance of these peaks suggested helical
molecular configuration (22). Thus, both the calculated and
experimental results supported the helical molecular configura-
tion of OPVCN–Me. In addition, the solid 1H NMR spectrum gave
further evidence. The resonance peaks at 3.52 and 3.12 ppm in
Figure 3. Trace a is the instrument response function; trace b is the fluorescence
decay of OPVCN–C12 in chloroform; and trace c is a mixture of dichloromethane–
acetonitrile (v/v, 1 : 3).
less emission bands were observed in emission spectra. In
addition, there was no mirror image relationship between the
absorption and fluorescence spectra. All these spectral features
indicated a strong intramolecular charge transfer process in these
systems. The positive solvatochromism in emission spectra con-
firmed the ICT effect in OPVCN–Me and OPVCN–C12 systems
(27–30).
In the absorption spectra of the two compounds, the band
centered at 470 nm was due to the ICT effect (31,32), and the
band around 378 nm was assigned to the p–p* transition. As
shown in the emission spectra, the emission bands of OPVCN–
C12 and OPVCN–Me in toluene solution exhibited vibrational
structure, while structureless ICT bands were observed in more
polar solvents. The quantum yields of both the compounds in
chloroform solutions were rather high: OPVCN–Me, 16.3%;
OPVCN–C12, 14.2%. Fluorescein in NaOH aqueous solution was
used as standard material, and was excited by 496.5 nm (33). As
shown in Fig. 3, the fluorescence decay time of OPVCN–C12 in
chloroform solution (20°C, t1 = 1.47 ns) can be fitted as single
exponentials without indication of a locally excited (LE) state. The
result demonstrated that an ICT reaction from an LE state to an
ICT state probably occurred in the solution (34,35). The decay
1
the solid H NMR spectrum of OPVCN–Me were attributed to
–OCH3, which indicated that the two –OCH3 groups were in dif-
ferent chemical environments. This result supported the twisted
conjugated skeleton of OPVCN–Me molecules. As in the molecule
of OPVCN–Me, four strong electron-withdrawing cyano groups
were conjugated linked to OPV core, inducing strong charge
transfer and a twisted conjugation skeleton (23–26). No specific
resonance peaks were observed in the solid 13C NMR and 1H NMR
spectra of OPVCN–C12, which supported the symmetric molecu-
lar configuration of OPVCN–C12. Comparing the structures and
configurations of OPVCN–Me and OPVCN–C12, it was not hard to
find that the steric hindrance generated by dodecyl substantially
influenced the configuration of the conjugation skeleton.
The cyano groups were conjugated linked to the OPV core,
which resulted in the p-conjugation extension, electron delocal-
ization and strong ICT effect in the systems. As exhibited by DFT
calculation, a large overlap between the ground and the excited
state could be observed, indicating large electron delocalization
in the acceptor–p–acceptor molecular system (as shown in
Figure 1E, F). Figure 2 shows the absorption and emission spectra
of OPVCN–Me and OPVCN–C12 in different solvents. Several
spectral features were observed in the spectral study of
OPVCN–Me and OPVCN–C12. In toluene solution, both the emis-
sion bands of OPVCN–Me and OPVCN–C12 showed shoulder
bands. When in chloroform, ethyl acetate, acetone and acetoni-
trile solutions, large Stocks’ shifts and broad and fairly structure-
time of OPVCN–C12 in
a mixture of dichloromethane–
acetonitrile (v/v, 1:3) solution (t1 = 0.36 ns, single exponentials)
was much shorter than that in pure chloroform solution, which
indicated the existence of unstable excited states and stronger
intramolecular charge transfer process in OPVCN–C12 in a
dichloromethane–acetonitrile (v/v, 1:3) solution. The study of
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J. Lv et al.
Figure 4. The absorption (A) and emission (B) spectra of OPVCN–C12 (1 ¥ 10-5 M) with successive addition of Cu2+
ions (0–4.9 ¥ 10-5 M). The fluorescence intensity of OPVCN–C12 vs [Cu2+] is shown in the insert part of (B). (C) The
absorption spectra of OPVCN–C12 (1 ¥ 10-5 M) in the presence of Ca2+, Ni2+, Co3+, Zn2+, Cd2+, Pb2+, Hg2+, Fe3+ and Ag+
([metal ion] = 50 ¥ 10-5 M), Cu2+ ions (1 ¥ 10-5 M). (D) Photograph of OPVCN–C12 in dichloromethane–acetonitrile (v/v,
1 : 3) by addition of various ions.
fluorescence lifetime of OPVCN–C12 in different solvents showed
that solvents had an important influence on the intramolecular
ICT process of the compounds; the ICT process could be intensi-
fied by a polar solvent accompanied by a decrease in fluores-
cence intensity. Similar processes occurred in OPVCN–Me as well.
10-5 M) in a mixture of dichloromethane–acetonitrile solution
(v/v, 1:3) with successive addition of Cu2+ ions (0–4.9 ¥ 10-5 M) at
room temperature. The ICT band centered at 475 nm gradually
decreased with the formation of a new band centered at 326 nm.
In the measurement of fluorescence spectra, a significant
decrease in fluorescence intensity of OPVCN–C12 was detected
with the addition of Cu2+ ions (Fig. 4B). The changes in absorption
and emission spectra were probably caused by the formation of
OPVCN–C12/Cu (II) complex. With the help of polar solvents, elec-
trons concentrated on cyano groups, which permitted the
OPVCN–C12 molecules complex with metal ions. The ICT effect of
OPVCN–C12 molecule was reduced when binding with Cu2+ ions
and electron separation occurred in the molecules of PVCN–C12,
which explained the absorption and emission spectral changes.
OPVCN–C12 showed high selectivity and sensitivity to Cu2+ ions.
As shown in Fig. 4(C), minor changes were observed in the
absorption spectra of OPVCN–C12 solution with the addition of
Ca2+, Ni2+, Co3+, Zn2+, Cd2+, Pb2+, Hg2+, Fe3+ and Ag+ ions ([metal ion]
= 50 ¥ 10-5 M). Under identical condition, the addition of Cu2+ ions
resulted in conspicuous changes in the absorption band of
OPVCN–C12. The color change and fluorescence quenching can
be observed in the photograph shown in Fig. 4D. The detection
limit of OPVCN–C12 for Cu2+ ions was about 4 ¥ 10-7 M.
Metallo-response
The metallo-response of OPVCN–C12 and OPVCN–Me in toluene
and chloroform solution was studied. The results showed that
both the compounds were unable to interact with metal ions,
including Ca2+, Ni2+, Co3+, Zn2+, Cd2+, Pb2+, Cu2+, Hg2+, Fe3+ and Ag+
ions.We also tried to use the polar solvent for sensing those metal
ions. In a solution of acetonitrile, the emision spectra showed that
the fluorescence intensity of OPVCN–C12 and OPVCN–Me was
significantly quenched. This was due to the high charge concen-
tration distribution on cyano groups as a result of the solvent
effect, which resulted in an increase in metal-ion-binding ability
of cyano groups (36). A mixture of dichloromethane–acetonitrile
(v/v, 1:3) was applied as a solvent for detecting metal ions. Both
the compounds in the mixture solvent were orange-red solu-
tions, and the emission bands centered around 650 nm. The
results of sensing experiments showed that the OPVCN–C12
could selectively interact with Cu2+ ions in the presence of Ca2+,
Ni2+, Co3+, Zn2+, Cd2+, Pb2+, Cu2+, Hg2+, Fe3+ and Ag+ ions, while
OPVCN–Me could interact with Cu2+ and Fe3+ ions respectively.
By addition of the metal ions to a solution of OPVCN–C12 in a
mixture of dichloromethane–acetonitrile (v/v, 1 : 3), only Cu2+
ions could result in spectral changes of OPVCN–C12. Figure 4(A)
shows the absorption spectral changes of OPVCN–C12 (1 ¥
The formation of the charge transfer complex of OPVCN–
C12/Cu (II) could be effectively supported by FTIR spectra. In FTIR
spectra, the stretching vibration of CN for OPVCN–C12 was
observed at 2222 cm-1. When Cu2+ ions were added into a solu-
tion of OPVCN–C12 in a mixture of dichloromethane–acetonitrile
(v/v, 1:3), a charge transfer band of CN for OPVCN–C12/Cu (II)
complex was observed at 2307 cm-1 in FTIR spectra (37).
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Luminescence 2011; 26: 185–190

Two novel cyano-containing oligo(phenylene-vinylene) derivatives
Figure 5. The fluorescence emission spectra and absorption spectra (inserts) of OPVCN–Me (1 ¥ 10-5 M) with Cu2+ ions
(0–4.2 ¥ 10-5 M) (A) and Fe3+ ions (0–5.6 ¥ 10-5 M) (B) successive additions.
However, the 2222 cm-1 band was still observed even when large
Supporting information
extra Cu2+ ions were added, which indicated weak binding
Supporting information can be found in the online version of this
article.
between OPVCN–C12 and Cu2+ ions.
In order to understand the formation process of OPVCN–
C12/Cu (II) complex, a modified method for determination coor-
dination number was taken into consideration (38,39; K. Hirose,
spreadsheet software; simple instruction for this software is
shown on the sheet). By employing this method, we estimated
the coordination number for OPVCN–C12/Cu (II) complex based
on absolute concentrations of the components and the absor-
bance variations at 475 nm. As the calculated result showed, the
x-coordinate at the maximum in the curve is in the range 0.3–
0.35, which supports the 1:2 complex of OPVCN–C12/Cu (II). The
stoichiometry and the coordination nature of Cu2+ ions estab-
lished the formation of the 1:2 OPVCN–C12–Cu2+ complex.
To a solution of OPVCN–Me in a mixture of dichloromethane–
acetonitrile (v/v, 1:3) were added various metal ions, such as
Ca2+, Ni2+, Co3+, Zn2+, Cd2+, Pb2+, Cu2+, Hg2+, Fe3+ and Ag+ ions; both
Cu2+ and Fe3+ ions could result in color change and fluorescence
quenching of the solution. In the Cu2+ ions titration experiment,
gradual spectral changes were observed, and the titration ended
at the molar ratio of 4.2:1, [Cu2+]: [OPVCN–Me] (Fig. 5A). When Fe3+
ions were titrated into the solution of OPVCN–Me in a mixture
of dichloromethane–acetonitrile (v/v, 1:3), mutations were
observed in absorption and emission spectra. When the molar
ratio of Fe3+ to OPVCN–Me changed from 0 to 4.8, the spectra
showed a minor change. However, further addition of Fe3+ ions
(molar ratio, 5.6:1) induced dramatic a decrease in the ICT band
and the fluorescence intensity was significantly quenched
(Fig. 5B). These results showed that the metallo-responses of
OPVCN–Me are quite different from those of OPVCN–C12, and
the differences are most probably caused by the different alkyl
chains on substituted OPV.
Acknowledgment
This work was supported by the National Nature Science Foun-
dation of China (20873155 and 20831160575), the National Basic
Research 973 Program of China and the Chinese Academy of
Sciences – Croucher Foundation Funding Scheme for Joint
Laboratories.
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