Synthesis and Properties of Polythiophenes

with Conjugated Side-Chains Containing

Carbon–Carbon Double and Triple Bonds
ERJUN ZHOU,1,2 JIANHUI HOU,1,2 CHUNHE YANG,1 YONGFANG LI1
1
CAS Key Laboratory of Organic Solids, Center for Molecular Science, Institute of Chemistry,
Chinese Academy of Sciences, Beijing 100080, China
2
Graduate School, Chinese Academy of Sciences, Beijing 100039, China

Received 30 October 2005; accepted 15 January 2006

DOI: 10.1002/pola.21338
Published online in Wiley InterScience (www.interscience.wiley.com).

ABSTRACT: Two soluble side-chain conjugated polythiophenes, poly{3-[2-(4-octyloxy-

phenyl)-vinyl]-thiophene} (P3OPVT) and poly{3-(4-octyloxy-phenylethynyl)-thiophene}
(P3OPET) have been synthesized successfully. In P3OPVT and P3OPET, substituted
benzene rings are connected with the polythiophene backbone through trans carbon–
carbon double bond and carbon–carbon triple bond, respectively. Absorption spectra
of the P3OPVT and P3OPET both show two absorption peaks located in UV and visi-
ble region, respectively. The results of optical and electrochemical measurements
indicate that the conjugated side-chains can reduce the bandgap effectively. This type
of side-chain conjugated polythiophenes may be promising for the applications in poly-
mer photovoltaic cells and field effect transistors. V
C 2006 Wiley Periodicals, Inc. J Polym Sci

Part A: Polym Chem 44: 2206–2214, 2006

Keywords: conjugated polymers; conjugated side-chain; GRIM method; synthesis;
UV–vis absorption spectrum.

INTRODUCTION ing the polydispersity5; (2) attaching the side-

chains with special functional groups6–9; (3)
Among p-conjugated polymers, poly((3-substi- changing the end groups of the backbone10,11; and
tuted)-thiophenes) are promising candidates for (4) copolymerizing with other monomers.12,13
polymer light-emitting diodes, polymer field ef- However, in most of these works, the side-
fect transistors, and polymer solar cells because chains are only used to improve solubility of the
they are environmentally stable, highly process- polymers or as a bridge to link with functional
able, and exhibit relatively higher charge carrier groups, few reports exist on improving the conju-
mobility and electrical conductivity.1–4 To im- gation of polythiophenes through the side-chains.
prove their properties for fulfilling different ap- Undoubtedly, the increase of conjugation degree
plication requirements, chemical modifications of will be desirable for improving various properties
poly((3-substituted)thiophenes) have been per- of the p-conjugated polymers. In 1999, M. R.
formed actively in recent years. These works Andersson’s group synthesized a class of phenyl-
mostly focused on (1) improving the regioregular- substituted polythiophene using FeCl3 method.14
ity, increasing the molecular weight and decreas- However, because the phenyl ring in the side
chain is directly linked with thiophene backbone,
Correspondence to: Y. Li (E-mail: [email protected])
the big steric hindrance results in poor coplanar-
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 44, 2206–2214 (2006)
ity. Hence, we choose CH¼ ¼CH double bond and
V
C 2006 Wiley Periodicals, Inc. CBC triple bond to link the octyloxy-substituted
2206
 SIDE-CHAINS CONJUGATED POLYTHIOPHENES 2207

phenyl ring and thiophene backbone to get new 4-Octyloxy-benzaldehyde (1)

conjugated side-chain polythiophenes.
To a 250-mL three-necked round-bottom flask
Because the CH¼ ¼CH double bond and CBC
equipped for stirring, 4-hydroxy-benzaldehyde
triple bond are unstable in many reactions, it is
(12.2 g, 0.10 mol), DMF (100 mL), anhydrous po-
difficult to get this class of polythiophene deriva-
tassium carbonate (13.8 g, 0.10 mol), and 1-n-bro-
tives through common method of obtaining
mooctane (19.3 g, 0.10 mol) were added. The solu-
poly(3-alkylthiophenes) or through FeCl3 method.
tion was stirred and heated to reflux for 5 h and
Recently, our group have developed a synthesis
then poured into cool water. The mixture was
process to get poly{3-[2-(4-(2-ethylhexyloxy)-phe-
extracted with ether, and the organic layers were
nyl)-vinyl]-thiophene} with conjugated side-chain
collected, washed with water, and dried over an-
containing CH¼ ¼CH double bond.15 Now, we syn-
hydrous MgSO4. The solvent was removed under
thesized another side-chain CH¼ ¼CH double
reduced pressure, and the distillation under vac-
bond-containing polythiophene derivative and
uum afforded compound 1 as a colorless oil (21 g,
changed the CH¼ ¼CH double bond to CBC triple
90%). Ms: m/z ¼ 234[Mþ]. 1H NMR (CDCl3, ppm,
bond to get the polythiophene derivative with the
d): 9.87 (s, 1H, CHO), 7.82 (d, 2H, Ar H), 6.97 (d,
conjugated side-chain containing CBC triple
2H, Ar H), 4.03 (t, 2H, OCH2), 1.80 (m, 2H, CH2),
bond. The optical and electrochemical properties
1.45–1.28 (m, 10H, 5
CH2), 0.89 (t, 3H, CH3).
of these two polythiophenes are also reported in
this article.
(2,5-Dibromo-thiophene-3-ylmethyl)-phosphonic
EXPERIMENTAL acid diethyl ester (2)
Compound 2 has been synthesized before,15 now
Materials and Measurements. the crude product was purified by flash column
CH3MgBr and Ni(dppp)Cl2 were obtained from chromatography eluting with petroleum ether/
Alfa and Aldrich Chemical Co. and were used as ethyl acetate (1:1). After purification, compound 2
received. THF was dried over Na/benzophenone was recovered as a pale yellow oil (23.5 g, 75%
ketyl and freshly distilled prior to use. DMF and yield). Ms: m/z ¼ 390(Mþ). 1H NMR (CDCl3,
1-bromo-octane were dried over molecular sieves ppm, d): 7.00 (s, 1H, Th H), 4.08 (m, 4H, 2

and freshly distilled prior to use. The other mate- OCH2), 3.10 (d, 2H, CH2), 1.29 (t, 6H, 2
CH3).
rials were common commercial level and used as
received. 2,5-Dibromo-3-[2-(4-octyloxy-phenyl)-vinyl]-thio-
1
H NMR spectra were measured using a phene (3)
Bruker DMX-300 spectrometer. Absorption spec-
tra were taken on a Hitachi U-3010 UV–vis spec- Under an ice–water bath, compound 2 (7.84 g,
trophotometer. Photoluminescence spectra were 0.02 mol) was dissolved in 50 mL DMF and
recorded on a Hitachi F-4500 spectrophotometer. CH3ONa (1.2 g, 0.022 mol) was added. After
The molecular weight of polymers was measured 5 min, compound 1 (4.68 g, 0.02 mol) was added
by GPC method, and polystyrene was used as a dropwise to the solution. After 2 h, the solution
standard. The electrochemical cyclic voltammetry was poured into methanol, filtered, and recrystal-
(CV) was conducted on a Zahner IM6e Electro- lized with methanol to afford compound 3 as a
chemical Workstation. The CV was performed in white powder (6.6 g, yield 70%). Ms: m/z ¼ 470
an acetonitrile solution of 0.1 mol/L [Bu4N]PF6 [Mþ]. 1H NMR (CDCl3, ppm, d): 7.42 (d, 2H, Ar
(Bu ¼ butyl) at a scan rate of 0.1 V/s at room tem- H), 7.19 (s, 1H, Th H), 6.88 (d, 2H, Ar H), 6.85(s,
perature under the protection of argon. A Pt plate 2H, CH¼ ¼CH), 3.97 (t, 2H, OCH2), 1.79 (m, 2H,
coated with a thin polymer film was used as the CH2), 1.29–1.49(m, 10H, 5
CH2), 0.89 (t, 3H,
working electrode. A Pt wire and an Ag/Agþ elec- CH3). ELEM. ANAL. Calcd for C20H22OSBr2: C,
trode were used as the counter electrode and ref- 50.86%; H, 5.12%. Found: C, 50.63%; H, 5.13%.
erence electrode, respectively.
2,5-Dibromo-3-(4-octyloxy-phenylethynyl)-
Synthesis of Monomers and Polymers thiophene (4)
The synthetic routes of the monomers and poly- To a solution of compound 3 (4.72 g, 0.01 mol) in
mers are shown in Scheme 1. CCl4 (40 mL) was added bromine (0.57 mL, 0.011
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2208 ZHOU ET AL.

Scheme 1. Synthetic routes of the monomers and polymers.

mol) with stirring at room temperature. After 1.29–1.54 (m, 10H, 5
CH2), 0.88 (t, 3H, CH3).
30 min, the solution was poured into water and ELEM. ANAL. Calcd for C20H22OSBr2: C, 51.08%;
washed with solution of KOH until the oil organic H, 4.72%. Found: C, 51.19%; H, 4.78%.
layer become colorless, then the organic layer
was dried over anhydrous MgSO4, filtered, and
concentrated. P3OPVT
To the product without any purification Under N2, monomer 3 (0.944 g, 2 mmol) was dis-
directly added the solution of KOH (4.48 g, 0.08 solved in freshly distilled THF (13 mL, resulting in
mol) dissolved in ethanol (100 mL), this mixture a 0.15 mol/L solution). To this solution was added
was heated under reflux with stirring for 24 h. methylmagnesium bromide (0.65 mL, 2.05 mmol).
The reaction mixture was then poured into cold The mixture was heated to reflux for 2 h.
water and extracted with CHCl3. The organic Ni(dppp)Cl2 (11 mg, 1 mol %) was added and the
layer was washed with water and then dried over solution was stirred overnight. The mixture was
anhydrous MgSO4, filtered, and concentrated. poured into 100 mL of methanol and then filtered
The crude product was purified by flash column into a Soxhlet thimble. Soxhlet extractions were
chromatography eluting with petroleum ether/ performed with methanol, hexane, and CHCl3. The
ethyl acetate (30:1). The obtained product was polymer was recovered from the CHCl3 fraction by
recrystallised with methanol/ petroleum ether rotary evaporation. The final polymer was dried
(20:1) to afford compound 4 as a white powder under vacuum overnight (0.263 g, Yield ¼ 42%).
(2.12 g, yield 45%). Mn ¼ 12,558, Mw/Mn ¼ 1.96. 1H NMR (CDCl3,
Ms: m/z ¼ 468 [Mþ]. 1H NMR (CDCl3, ppm, d): ppm, d): 7.52–7.27(b, 2H), 7.06–6.70(m, 5H),
7.45 (d, 2H, Ar H), 7.00 (s, 1H, Th H), 6.87 (d, 2H, 3.98–3.85(b, 2H), 1.78–1.29(m, 12H), 0.88(s, 3H).
Ar H), 3.97 (t, 2H, OCH2), 1.79 (m, 2H, CH2), ELEM. ANAL. Calcd for (C20H24OS)n: C, 76.88%; H,
Journal of Polymer Science: Part A: Polymer Chemistry
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 SIDE-CHAINS CONJUGATED POLYTHIOPHENES 2209

1
Figure 1. H NMR spectra of monomer 3 and monomer 4.

7.74%; O, 5.12%; S, 10.26%. Found: C, 75.62%; H, 3.90(b, 2H), 1.77–1.25(m, 15H), 0.89(s, 3H). Elem.
7.84%; O, 4.90%; S, 8.97%; Br, 1.2%. Anal. Calcd for (C20H22OS)n: C, 77.38%; H,
7.14%; O, 5.15%; S, 10.33%. Found: C, 74.58%; H,
7.30%; O, 5.01%; S, 8.99%; Br, 3.1%.
P3OPET
RESULTS AND DISCUSSION
The polymerization process was the same as that
for P3OPVT, except that compound 4 was used
Synthesis and Characterization
instead of compound 3 (0.186 g, Yield ¼ 30%).
Mn ¼ 3381, Mw/Mn ¼ 2.14. 1H NMR (CDCl3, Scheme 1 shows the synthetic routes of P3OPVT
ppm, d): 7.50–7.25(b, 2H), 6.94–6.85(b, 3H), 3.97– and P3OPET. First, we add bromine in the 2- and
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2210 ZHOU ET AL.

Figure 2. (A) UV–vis absorption of P3OPVT, P3OPET, monomer 3, and monomer 4

in chloroform with the concentration of about 0.02 mg/mL. (B) Normalized PL spectra
of P3OPVT and P3OPET in chloroform.

5-position of the thiophene to get (2,5-dibromo- But for poly(3-arylthiophene)s, because of the
thiophene-3-ylmethyl)-phosphonic acid diethyl. chemical shift of protons on the phenyl ring are
Second, we get monomer 3 via Wittig–Hornor close to that of the protons on the 4-position on
reaction by coupling of (2,5-dibromo-thiophen-3- the thiophene ring, the regioregularity only can
ylmethyl)-phosphonic acid diethyl and 4-octyloxy- be determined by the signal of the CH2 groups on
benzaldehyde,15,16 Third, we change the CH¼ ¼CH the side chains closet to the phenyl ring.14
double bond to CBC triple bond to get monomer 4 For P3OPVT and P3OPET, since the CH2
through adding 1 mol Br2 and removing 2 mol groups on the side chains are far from the back-
HBr.17 To our knowledge, this is the first time the bone, the head-to-head coupling may have no
CH¼ ¼CH double bond between the substituted obvious influence on the chemical shift of protons
thiophene ring and substituted benzene rings of CH2 groups. Thus, although there is no obvious
change to CBC triple bond successfully, which head-to-head coupling signal, we cannot say
will enhance the possibility of obtaining new com- P3OPVT and P3OPET are fully regioregular.
pounds containing CBC triple bond. Finally, we Now, we are looking for other credible method to
polymerize monomer 3 and monomer 4 to get determine the regioregularity of these conjugated
P3OPVT and P3OPET via GRIM method, respec- side-chain polythiophenes.
tively.18 The solubility of P3OPET is poorer than that of
Figure 1 shows the 1H NMR spectra of monomer P3OPVT, which may be due to the stronger rigid-
3 and monomer 4. For monomer 3, there is no ity of CBC triple bond. A portion of P3OPET was
obvious cis-isomer signal, which indicates that insoluble in Soxhlet extractions with CHCl3, so
monomer 3 is all trans-isomer. When CH¼ ¼CH dou- the yield and molecular weight of P3OPET are
ble bond is changed to CBC triple bond and mono- lower than that of P3OPVT.
mer 3 is changed to monomer 4, the two protons in
vinyl unit at 6.85 ppm disappear completely.
Usually, the regioregularity of poly(3-alkylthio- Optical Properties
phene)s is estimated by comparing signal of the The UV–vis absorption spectra of P3OPVT,
protons on the 4-position on the thiophene ring.19 P3OPET, monomer 3, and monomer 4 in chloro-
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 SIDE-CHAINS CONJUGATED POLYTHIOPHENES 2211

form solutions are shown in Figure 2. The absorp- For the reason of the 86 nm redshift of the p-p*
tion maximum of monomer 3 is at 325 nm. When absorption peak of P3OPET in comparison with
CH¼ ¼CH double bond is changed to CBC triple that of P3OPVT, we think that the steric hin-
bond and monomer 3 is changed to monomer 4, drance is less and the coplanarity may be better
the absorption shows two peaks at 264 nm and at for the triple-bond substituted P3OPET than that
around 301 nm, respectively, in the UV region. of the double-bond substituted P3OPVT, so the
There is no any absorption in the visible region effective conjugation degree of P3OPET is greater
for the two monomers. While the UV–vis absorp- than that of P3OPVT.
tion spectra of P3OPVT and P3OPET both have Photoluminescence (PL) spectra of the two pol-
two absorption peaks, one is in the visible region ymers in CHCl3 solution are also shown in Figure
and another in the UV region. In comparison with 2. The polymers are excited at the wavelength
the monomer absorption, obviously, the absorp- corresponding to the maximum absorption of the
tion peak in UV region is attributed to the conju- p-p* transition. The maximum emission peaks of
gated side-chains, and the absorption in the visi- the P3OPVT and P3OPET are 578 nm and
ble region should be attributed to p-p* transition 598 nm, respectively. The redshift of the PL of
of the conjugated polymer main chains. For P3OPET may also be attributed to the increase of
P3OPET, the visible absorption is a rather broad- effective conjugated length.
band with maximum at 535 nm, 86 nm red- Figure 3 shows the UV–vis absorption spectra
shifted in comparison with that of P3OPVT (kmax of P3OPVT and P3OPET films on a quartz plate.
¼ 449 nm), and a long tail of the absorption In comparison with the absorption spectra of the
extends up to 750 nm. Corresponding to the dif- polymer solutions in CHCl3, the visible absorp-
ference of the absorption, the color of P3OPVT tions become stronger and red-shifted, similar to
and P3OPET in chloroform solutions is obviously the case of poly(3-hexylthiophene) where a p-
different, P3OPVT is red, but P3OPET is purple. stacked structure in the solid state formed.20 For
It is very infrequent for poly((3-substituted)thio- P3OPVT, the visible absorption peak of film red-
phenes) to show the color of purple. shifted by 82 nm from 449 nm to 531 nm in com-

Figure 3. UV–vis absorption spectra of P3OPVT and P3OPET films on a quartz

plate.
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2212 ZHOU ET AL.

Figure 4. Cyclic voltammograms of P3OPVT and P3OPET films on platinum plates

in an acetonitrile solution of 0.1 mol/L [Bu4N]PF6 (Bu ¼ butyl) with a scan rate of
0.1 V/s.

parison with its solution. For P3OPET, the red- Electrochemical Properties
shift is only 14 nm from 535 nm to 549 nm. For
The electrochemical behavior of the P3OPVT
these polymers containing big side chains, prob-
and P3OPET is investigated by cyclic voltam-
ably, the steric hindrance of side chains make the
metry (CV). As shown in Figure 4, the cyclic
polymer main chains distorted in solution, so that
voltammograms of the polymers show similar
the main chain absorption is weak and appears at
short wavelength. In the solid film, the interchain reversible p-doping/dedoping (oxidation/re-
interactions make the main chains extended and reduction) and n-doping/dedoping (reduction/re-
the conjugation degree increased, which enhan- oxidation) processes. The electrochemical n-dop-
ces the visible absorption and makes the absorp- ing (reduction) of P3OPVT and P3OPET starts
tion red-shifted.21 Correspondingly, the extent of at about 1.94 and 1.80 V vs. Ag/Agþ and
the redshift of the visible absorption of P3OPET shows reduction peaks at 2.39 and 2.09 V vs.
is less than that of P3OPVT, because of the less Ag/Agþ, respectively. The corresponding n-
distortion of main chain of P3OPET in solution. dedoping peaks of P3OPVT and P3OPET appear
But for the poly{3-(4-octyloxy-phenyl)-thio- at 2.01 and 1.86 V vs. Ag/Agþ, respectively.
phene}, in which octyloxy-substituted phenyl is Electrochemical p-doping (oxidation) of the pol-
connected with the thiophene backbone directly, ymers P3OPVT and P3OPET starts at about
p-p* absorption peak of film is only at 408 nm.14 0.21 and 0.17 V vs. Ag/Agþ and shows p-doping
The 123 nm (531 nm–408 nm) redshift for peaks at 0.61 and 0.56V vs. Ag/Agþ, respec-
P3OPVT and 141nm (549 nm–408 nm) redshift tively.
for P3OPET also indicate that the CH¼ ¼CH dou- It is well known that the onset potentials of the
ble bond and CBC triple bond can effectively p- and n-doping are corresponding to the HOMO
increase the conjugation degree of the polythio- and LUMO energy levels of the conjugated poly-
phene derivatives. mers.22,23 So, we can get the HOMO and LUMO
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 SIDE-CHAINS CONJUGATED POLYTHIOPHENES 2213

Table 1. The Optical and Electrochemical Properties of P3OPVT and P3OPET

UV–Vis Absorption Spectra Cyclic Voltammograms

In CHCl3 In Film p-Doping n-Doping

kmax kmax konset Eopt

g Eox
on HOMO Ered
on LUMO EEC
g
Polymer (nm) (nm) (nm) (eV) (V) (eV) (V) (eV) (eV)

P3OPVT 328, 449 316, 531 654 1.90 0.21 4.92 1.94 2.77 2.15
P3OPET 282, 535 284, 549 750 1.65 0.17 4.88 1.80 2.91 1.97

energy levels of P3OPVT and P3OPET, according chain conjugated polythiophenes are currently in
to the equations23: progress and will be reported in due course.

HOMO ¼ eðEox
on þ 4:71Þ ðeVÞ; This work was supported by NSFC (Nos. 50373050,
20373078, 20474069, 20421101, 20574078, and
LUMO ¼ eðEred
on þ 4:71Þ ðeVÞ:
60440420149) and the Ministry of Science and Tech-
nology of China (973 project, No. 2002CB613404).
For comparing expediently, the optical and
electrochemical data were listed in Table 1. From
Table 1, we can see that the HOMO is increased
and the LUMO is decreased from P3OPVT to REFERENCES AND NOTES
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