New p-Conjugated Polyaryleneethynylenes Containing a

1,3,5-Triazine Unit in the Main Chain: Synthesis and

Optical and Electrochemical Properties
QIANG FANG, SHIJIE REN, BING XU, JUNPING DU, AMIN CAO

Laboratory for Polymer Materials, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
354 Fenglin Road, Shanghai 200032, People’s Republic of China

Received 21 December 2005; accepted 3 April 2006

DOI: 10.1002/pola.21485
Published online in Wiley InterScience (www.interscience.wiley.com).

ABSTRACT: A series of new p-conjugated poly(aryleneethynylene)s containing a 1,3,5-

triazine unit in the main chain were synthesized in yields higher than 70% by poly-
condensation between dibromophenyl-1,3,5-triazine monomers and alkyl-substituted
diethynylbenzene (or diethynylfluorene) comonomers with Pd(PPh3)4 and CuI as cata-
lysts in the presence of triethylamine. The polymers had a number-average molecular
weight in the range of 5000–10,000 and showed good solubility in common organic
solvents. The polymers were photoluminescent both in solutions and in the solid
state. X-ray diffraction patterns of the powders of the polymers revealed that the
polymers were semicrystalline. Electrochemically, the polymers appeared to be re-
versible under reduction. V C 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44:

3797–3806, 2006
Keywords: conjugated polymers; electrochemistry; luminescence; polyaryleneethy-
nylenes; triazine derivatives

INTRODUCTION However, these aryl heterocyclic units at-

As a class of important p-conjugated polymers,
polyaryleneethynylenes (PAEs) have been well
investigated in the past 2 decades because of
their potential applications in electronic and pho-
tonic devices.1 In recent years, there has been
increasing interest in the synthesis and chemical
properties of PAEs possessing aryl heterocyclic
units such as carbazole,2 quinoline,3 thiophene,4
porphyrin,5 benzothiadiazole,6 quinoxaline,6(d) 8-
quinolinol,7 and silole units.8 These PAEs usually
show such functional properties as helical chiral-
ity,9 photoluminescence (PL),1 electrolumines-
cence,4 and optical nonlinearity.4(a)
Correspondence to: Q. Fang (E-mail: qiangfang@yahoo.com)
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 44, 3797–3806 (2006)
V
C 2006 Wiley Periodicals, Inc.
tached to p-conjugated PAEs do not include 1,3,5-
triazine rings. Actually, although several
reports10–15 have discussed the investigation of
p-conjugated polymers possessing 1,3,5-triazine
units in the main chain, p-conjugated PAEs
including 1,3,5-triazine rings have not attracted
attention. Nonconjugated polymers and supramo-
lecules containing 1,3,5-triazine units have
received much attention in industry because of
their high thermal stability derived from the
structural symmetry of 1,3,5-triazine units.16–18
Recent investigations indicate that some 1,3,5-
triazine-contaning oligomers or polymers exhibit
good optical and electrical properties.19–28 Struc-
turally, a 1,3,5-triazine unit is a typical electron-
accepting unit, and introducing a 1,3,5-triazine
unit into the main chain of conjugated polymers
is expected to improve the electron-injection and
-transportation ability of the polymers;20,27 such
3797
3798 FANG ET AL.
Chart 1. Chemical structures of the new polymers.
properties are useful in optic–electrical devices,
such as organic light-emitting diodes.20,23,27
Recently, one of the chief research interests in
conjugated polymers has been the modification of
their spectral and electrical properties by the
introduction of certain functional groups to the
main chains of the polymers. For this purpose, we
have already investigated several p-conjugated,
1,3,5-triazine-based polymers.14 As an extension
of that research, we have designed and synthe-
sized four new PAE-type polymers containing a
1,3,5-triazine unit in the main chain (P1–P4), as
shown in Chart 1. Here we report the results.
EXPERIMENTAL
Materials
All starting materials were purchased from
Aldrich Co. and used as received. Monomers Ma
and Mb were synthesized by the previously
reported method.14 1,4-Bis(dodecyloxy)benzene
was prepared according to a procedure reported
in the literature.29 All solvents were dehydrated
and distilled under an inert atmosphere before
use.
Instruments
Fourier transform infrared (FTIR) spectra were
recorded on a Nicolet spectrometer with NaCl pel-
lets. Elemental analysis was taken with a Carlo
Erba 1106 elemental analyzer. 1H{13C} NMR
spectra were carried out on a Bruker DRX 400
spectrometer. A PerkinElmer Series 200 gel per-
meation chromatography (GPC) system was
employed to deduce the number-average molecu-
lar weight (Mn) and molecular weight distribu-
tion [weight-average molecular weight/number-
average molecular weight (Mw/Mn)] on the basis
of polystyrene standards, with tetrahydrofuran
Journal of Polymer Science: Part A: Polymer Chemistry
(THF) as the solvent and UV as the detector.
Ultraviolet–visible (UV–vis) and PL spectra were
obtained with a Hitachi UV-2800 and a Hitachi
F-4500 spectrophotometer. The thermal stability
was determined with a TA 2000 thermogravimet-
ric analyzer at a heating rate of 10 8C min
1 in
nitrogen. Cyclic voltammetry (CV) of cast films of
the polymers on Pt wires was performed in an
acetonitrile solution of [Bu4N]BF4 (0.10 M) under
an argon atmosphere with 0.10 M AgNO3/Ag and
a platinum wire as reference and counter electro-
des, respectively. A CHI 600B analyzer was used
for the measurements. The films of the polymers
on the surface of a glass or metal plate were pre-
pared by a general casting method. For example,
a solution of a polymer in toluene was adding
dropwise by a burette to the surface of a glass,
quartz, or platinum plate. A film was formed on
the surface after the evaporation of the solvent at
the ambient temperature. For the films on Pt
wires, they were prepared first by the immersion
of the end of a Pt wire in a solution of a polymer
in toluene and then by natural drying at the am-
bient temperature.
Synthesis of 1,4-Bis(dodecyloxy)-2,5-
dibromobenzene (1)
This compound was synthesized with a modifica-
tion of a literature method.29 A solution of bro-
mine (6.2 g, 39 mmol) in chloroform (20 mL) was
added dropwise to a solution of 1,4-bis(dodecyloxy)
benzene (3.6 g, 8 mmol) in 100 mL of chloroform
for 20 min. The deep red mixture was stirred for
1 h at room temperature before 100 mL of water
was added. The organic layer was washed with
aqueous NaHSO3, brine, and water and dried
over anhydrous Na2SO4. After filtration, the sol-
vent was evaporated to give a white, crystalline
solid, which was recrystallized from ethanol
to give pure 1 as white crystals (4.32 g, yield
¼ 89%).
DOI 10.1002/pola

1
H NMR (CDCl3, d): 7.09 (2H, s), 3.94 (4H, t),
1.79 (4H, m), 1.23–1.48 (36H, m), 0.88 (6H, t).
Synthesis of 1,4-Diethynyl-2,5-bis(dodecyloxy)
benzene (2)
This compound was synthesized with a modifica-
tion of a literature method.6(c) Pd(PPh3)4 (346 mg,
0.3 mmol), CuI (57 mg, 0.3 mmol), and 1 (1.933 g,
3.2 mmol) were charged under argon in a 250-mL
Schlenk tube with dry and degassed triethyl-
amine (50 mL). (Trimethylsilyl)acetylene (1.5 mL,
10.6 mmol) was then added to the tube, and the
reaction mixture was stirred and heated at 80 8C
under argon for 20 h. After being cooled to room
temperature, the mixture was filtered to elimi-
nate the ammonium salt, and the triethylamine
was removed under reduced pressure. The
obtained residue was purified by chromatography
(SiO2, CH2Cl2/hexane ¼ 1:4 v/v). 1,4-Bis(trime-
thylsilyl)ethynyl-2,5-bis(dodecyloxy)benzene was
obtained as a white solid (1.89 g, yield ¼ 92%).
To a stirring solution of 1,4-bis(trimethylsilyl)
ethynyl-2,5-bis(dodecyloxy)benzene (1.89 g, 3 mmol)
in dichloromethane (100 mL) were added K2CO3
(2.07 g, 15 mmol), ethanol (100 mL), and water
(50 mL). The mixture was stirred at room temper-
ature for 15 h. The organic layer was washed
with water until the pH was 7 and was dried over
anhydrous MgSO4. After the evaporation of the
solvent, the crude product was purified first by
chromatography (SiO2, CH2Cl2/hexane ¼ 1:10 v/v)
and second by recrystallization from acetone. 2
was obtained as white, needle crystals (930 mg,
yield ¼ 63%).
1
H NMR (CDCl3, d): 6.95 (2H, s), 3.96 (4H, t),
3.33 (2H, s), 1.78 (4H, m), 1.26–1.48 (36H, m),
0.88 (6H, t). FTIR (NaCl pellets, cm
1): 3286,
2922, 2849, 2105, 1501, 1463, 1385, 1273, 1219,
864, 644. ELEM. ANAL. Calcd. for C34H54O2: C,
82.59%; H, 10.93%. Found: C, 82.78%; H, 10.50%.
Synthesis of 2,7-Dibromo-9,9-dioctylfluorene (3)
To a degassed mixture including 2,7-dibromo-
fluorene (6.48 g, 20 mmol), tetrabutylammonium
bromide (TBAB; 644 mg, 2 mmol), and dimethyl
sulfoxide (DMSO; 60 mL) was added degassed
aqueous NaOH (30 mL, 50% w/w), and the
obtained solution was stirred at room tempera-
ture for 0.5 h. Then, 1-bromooctane (13.52 g,
70 mmol) was added to the mixture, and the
resulting solution was stirred at 35 8C for 5 h.
After 100 mL of water was added, the mixture
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola
-CONJUGATED POLYARYLENEETHYNYLENES 3799
was extracted twice with 200 mL of dichlorome-
thane. The combined organic layers were washed
with brine and dried over anhydrous Na2SO4.
After the evaporation of the solvent, the crude
product was purified by successive recrystalliza-
tion from hexane and ethanol to yield a white,
crystalline product in a yield of 86%.
1
H NMR (CDCl3, d): 7.52 (2H, dd), 7.43–7.46
(4H, m), 1.91 (4H, m), 1.10–1.25 (20H, m), 0.83
(6H, t), 0.59 (4H, m). ELEM. ANAL. Calcd. for
C29H40Br2: C, 63.51%; H, 7.35%. Found: C, 63.54;
H, 7.53%.
Synthesis of 2,7-Bis(ethynyl)-9,9-dioctylfluorene (4)
With a procedure similar to the preparation of 2,
4 was obtained in a yield of 91% after purification
by chromatography (SiO2, CH2Cl2/hexane ¼ 1:10
v/v).
1
H NMR (CDCl3, d): 7.63 (2H, d), 7.46–7.49
(4H, m), 3.15 (2H, s), 1.93 (4H, m), 1.03–1.25
(20H, m), 0.82 (6H, t), 0.57 (4H, m). FTIR (NaCl
pellets, cm
1): 3310, 2927, 2854, 2108, 1464, 822.
ELEM. ANAL. Calcd. for C33H42: C, 90.41%; H,
9.59%. Found: C, 90.47%; H, 9.49%.
Polymerization
P1 and P2
To a 250-mL Schlenk flask charged with 1,4-dido-
decyloxy-2,5-diethynylbenzene (0.5 mmol), Ma or
Mb (0.5 mmol), Pd(PPh3)4 (0.05 mmol), and CuI
(0.05 mmol), triethylamine (30 mL) and THF
(40 mL) were added under argon. The mixture
was stirred for 0.5 h at room temperature and
then heated at 80 8C for 72 h. After being cooled
to room temperature, the mixture was filtered to
eliminate the ammonium salt. After the evapora-
tion of the solvents, the resulting residue was
redissolved in 10 mL of chloroform, and the solu-
tion was poured into 200 mL of methanol to give
a polymer precipitate. P1 or P2 was obtained
as an orange powder by filtration and drying
in vacuo.
Yield: P1, 89%; P2, 73%. Molecular weight
(GPC, eluent ¼ THF): P1, Mn, 5000, Mw/Mn [poly-
dispersity index (PDI)], 1.81; P2: Mn, 7000, Mw/
Mn (PDI), 2.07. FTIR (NaCl pellets, cm
1): P1,
3062, 2922, 2204, 1587, 1513, 1368; P2, 3080,
2923, 2204, 1584, 1509, 1370. 1H NMR (CDCl3, d):
P1, 8.76 (4H, d), 8.66 (2H, d), 7.57–7.74 (7H, m),
6.97–7.10 (2H, m), 4.02 (4H, s), 1.84–1.93 (4H, m),
0.79–1.41(42H, m); P2, 8.75 (4H, d), 8.64 (2H, d),
7.70–7.75 (4H, m), 7.02–7.10 (4H, m), 3.95–4.10
3800 FANG ET AL.

Scheme 1. Synthetic route for the new polymers. The reagents and conditions are
as follows: (i) CHCl3 and Br2; (ii-a) trimethylsilylacetylene, Et3N, CuI, Pd(PPh3)4,
and 80 8C for 20 h; (ii-b) K2CO3 and ethanol; and (iii) DMSO, TBAB, NaOH (50% w/w),
and 1-bromooctane.

(7H, m), 1.81–1.91 (4H, m), 0.81–1.41 (42H, m).
13
C NMR (CDCl3, d): P1, 171.64, 171.12, 153.93,
135.99, 135.16, 132.73, 131.96, 131.84, 130.50,
129.02, 128.70, 127.59, 117.06, 92.65, 89.78, 69.74,
31.93, 29.76, 29.70, 29.52, 29.39, 29.21, 26.17,
26.00, 22.72, 22.68, 14.13; P2, 171.31, 170.87,
163.07, 153.92, 135.95, 135.08, 131.78, 130.94,
130.44, 128.80, 128.33, 117.30, 114.02, 92.53,
89.41, 69.76, 55.47, 31.94, 29.75, 29.70, 29.51,
29.39, 29.22, 26.17, 26.00, 22.72, 22.68, 14.09.
ELEM. ANAL. Calcd. for Br

(C55H65N3O21.8H2O)6

Br
(P1): C, 76.91%; H, 7.99%; N, 4.89%; Br, 3.11%.
Found: C, 76.75%; H, 7.91%; N, 3.93%; Br, 3.15%.
ELEM. ANAL. Calcd. for Br

(C56H67N3O31.8H2O)8

Br
(P2): C, 76.56%; H, 8.04%; N, 4.78%; Br, 2.27%.
Found: C, 76.29%; H, 7.93%; N, 4.28%; Br, 3.58%.
P3 and P4
The polymerization procedure of P3 and P4 was
similar to that of P1 and P2, except that the reac-
tion temperature was lowered to 60 8C.
Yield: P3, 92%; P4, 83%. Molecular weight
(GPC, eluent ¼ chloroform): P3, Mn, 10,000, Mw/
Mn (PDI), 1.88; P4, Mn, 9000, Mw/Mn (PDI), 2.03.
FTIR (NaCl pellets, cm
1): P3, 3065, 2926, 2207,
1597, 1514, 1369; P4, 3060, 2927, 2200, 1584,
1508, 1370; 1H NMR (CDCl3, d): P3, 8.65–8.80
(6H, m), 7.49–7.78 (13H, m), 1.95–2.03 (4H, m),
Journal of Polymer Science: Part A: Polymer Chemistry
1.09–1.25 (20H, m), 0.83 (6H, m), 0.57–0.68 (4H,
m); P4, 8.63–8.81 (6H, m), 7.55–7.80 (10H, m),
7.08–7.12 (2H, m), 3.95 (3H, s), 1.99–2.04 (4H,
m), 1.10–1.26 (20H, m), 0.79–0.88 (6H, m), 0.62–
0.66 (4H, m). 13C NMR (CDCl3, d): P3, 171.97,
171.26, 151.56, 141.21, 136.26, 135.90, 132.88,
131.99, 131.21, 129.18, 128.86, 127.84, 127.15,
126.31, 121.93, 120.41, 93.60, 89.92, 55.51, 40.56,
31.96, 30.19, 29.86, 29.39, 23.92, 22.76, 14.22; P4,
171.46, 170.85, 163.58, 151.30, 141.04, 135.95,
135.34, 131.90, 131.04, 130.46, 128.87, 127.52,
126.16, 121.80, 120.16, 114.07, 93.42, 89.82,
55.51, 55.40, 40.42, 31.82, 30.05, 29.72, 29.28,
23.79, 22.62, 14.08. ELEM. ANAL. Calcd. for
Br

(C54H53N31.2H2O)13

Br (P3): C, 83.41%;
H, 7.13%; N, 5.41%; Br, 1.58%. Found: C, 83.35%;
H, 7.21%; N, 4.70%; Br, 0.70%. ELEM. ANAL. Calcd.
for Br

(C55H55N3O1.8H2O)11

Br (P4): C,
80.49%; H, 7.15%; N, 5.12%; Br, 1.77%. Found: C,
80.06%; H, 7.02%; N, 4.75%; Br, 2.04%.
RESULTS AND DISCUSSION
Synthesis and Characterization of the Polymers
The synthetic route of the monomers and the cor-
responding polymers is shown in Scheme 1. The
four polymers, P1–P4, were synthesized from tri-
DOI 10.1002/pola
 -CONJUGATED POLYARYLENEETHYNYLENES 3801

Table 1. Synthesis Results and Optical Data for P1–P4

kmax (nm; UV–vis) kEM (nm; PL)c

Yield
Polymer (%) Mna Mw/Mn In Toluene (lg ed) In Filmse Egopt (eV)b In Toluene (Ff) In Filmse

P1 89 5,000 1.81 415 (4.54) 422 2.51 473 (49) 542

P2 73 7,000 2.07 402 (4.60) 424 2.46 471 (45) 540
P3 92 10,000 1.88 386 (4.75) 387 2.82 429 (66) 500
P4 83 9,000 2.03 382 (4.71) 386 2.79 425 (67) 503
a
Determined by GPC (with polystyrene standards).
b
Optical band gap estimated from the UV–vis absorption onset wavelength of P1–P4 in the solid state.
c
Position of the emission peak from PL data.
d
Molar absorption coefficient. The molarity is based on the repeating units of the polymers.
e
Cast onto a quartz glass plate at room temperature with toluene as the solvent.
f
PL quantum yield estimated with a 0.5 M H2SO4 solution of quinine (10
5 M, F ¼ 0.55) as a reference. In all cases, the
exciting wavelengths were UV–vis peaks of P1–P4.

azine monomers (Ma and Mb) and 2,5-didodecy- P2 and P4) in UV–vis absorption peaks may be
loxy-1,4-diethynylbenzene or 9,9-dioctyl-2,7-diethy- due to the presence of a charge-transfer (CT) elec-
nylfluorene with the Heck–Sonogashira polycon- tronic state in P1 (or P2) deriving from the inter-
densation reaction.30
The yields of the four polymers were higher
than 70%, and Mn of the polymers, determined by
GPC versus polystyrene standards, ranged from
5000 to 10,000, as shown in Table 1. P1–P4 were
orange powders and were easily dissolved in com-
mon organic solvents such as dichloromethane,
THF, and toluene. The films of the polymers made
by the casting method showed strong green PL
under the radiation of a UV lamp (365 nm).
The chemical structure of the polymers was
characterized by FTIR, 1H NMR, 13C NMR, and
elemental analysis. As can be seen in Figure 1,
the strong terminal m (CBC

H) vibration peak at
about 3290 cm
1 of the monomers (2 and 4) disap-
peared during the polymerization. Instead, P1–
P4 showed a m (CBC) peak representing disubsti-
tuted acetylene at about 2200 cm
1. The 1H NMR
spectra of the polymers are also shown in the Ex-
perimental section and Figure 2; this indicates
that all the detected peaks of the polymers and
ratios between their peak areas were consistent
with the proposed structure.

Optical and Thermal Properties and Crystallinity

UV–vis spectra of P1–P4 in toluene and in the
solid state are listed in Table 1. As a sample, Fig-
ure 3 gives the UV–vis spectra of P2 and P4 in
toluene and in the solid state. As can be seen in
Table 1 and Figure 3, P1–P2 showed UV–vis
absorption peaks at about 410 nm in toluene,
whereas P3 and P4 showed the peaks at about Figure 1. IR spectra of P1–P4 and corresponding
386 nm; such difference between P1 and P3 (or monomers 2 and 4 (T ¼ transmittance).
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola
3802 FANG ET AL.

Figure 2. 1H NMR spectra of P1–P4 and corresponding monomers 2 and 4 in CDCl3.

The single and double asterisks indicate CHCl3 and water in CDCl3, respectively.

action between an electron-accepting triazine peaks of P1 and P2 had a redshift of about 10 nm

unit and an electron-donating dialkyloxybenzene from those of their solutions in toluene. For P3
unit. In the solid state, the UV–vis absorption and P4, although their UV–vis maximum absorp-
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola

Figure 3. UV–vis spectra of P2 and P4 in toluene
and in the films.
tion peaks had no evident shift from solutions to
the films, the onset position of the UV–vis absorp-
tion bands of P3 and P4 were at longer wave-
length positions in the films than in the solutions.
These UV–vis data for P1–P4 suggest the pres-
ence of certain intermolecular interaction due to
the stacking of the polymers in the solid state.
From the UV–vis absorption onset wave-
lengths of P1–P4, their optical band gaps were
estimated,31 as summarized in Table 1, and they
suggested that an electron-donating

OCH3 in
the triazine ring brought about slight reduction
of the gap between the highest occupied molecu-
lar orbital and lowest unoccupied molecular or-
bital (LUMO).
PL spectra of P2 and P4 in toluene and in the
films are shown in Figure 4. The detailed PL data
for P1–P4 are summarized in Table 1. In toluene,
Figure 4. PL spectra of P2 and P4 in toluene and
in the films.
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola
-CONJUGATED POLYARYLENEETHYNYLENES 3803
Figure 5. TGA curves of P1–P4.
P1 and P2 and P3 and P4 showed maximum
emission peaks at about 470 nm and at about 420
nm, respectively, and this agreed with the onset
positions of the UV–vis absorption bands of the
polymers (see Fig. 3). As mentioned previously,
there was a CT electronic state in P1 (or P2); this
state made P1 or P2 show the emission peak at a
longer wavelength than that of P3 or P4.
As can be seen in Table 1, in toluene, the quan-
tum yields of P1 and P2 were lower than 50%,
whereas those of P3 and P4 were higher than
65%. Polymers with a donor–acceptor system
usually show lower quantum yields than poly-
mers without such a system.32 In our case, P1
and P2 exhibited lower quantum yields than P3
and P4, and this implied the presence of a CT sys-
tem in P1 and P2.
In the solid state, the maximum emission
peaks of P1–P4 changed to more than 500 nm,
indicating the existence of p stacking in the poly-
mers in the solid state. It is known that some
PAEs with an acceptor–donor system such as
PAEs consisting of electron-accepting benzothia-
Table 2. TGA Data for P1–P4
Weight-Loss Temperature (8C)a
Polymer T5 T10 T30
P1 392 410 458
P2 398 418 467
P3 361 431 514
P4 377 433 528
a
T5, T10, and T30 are the temperatures at which the
weight losses are 5, 10, and 30%, respectively.
3804 FANG ET AL.

Of the two types of aromatic units (1,3,5-tri-

azine and benzene or fluorene units), the 1,3,5-
triazine unit receives the reduction at a higher
potential (e.g., n-doping peak of 2,4,6-triphenyl-
1,3,5-triazine ¼
1.65 V20 vs Agþ/Ag) than the
benzene ring or fluorene unit [e.g., n-doping peak
of poly(p-phenylene) ¼
2.6 V33 and n-doping
peak of polyfluorene ¼ 2.3 V34,35 vs Agþ/Ag]. Con-
sequently, the reduction peaks of P1–P4 in Fig-
ure 4 are considered to be mainly concerned with
the reduction of the 1,3,5-triazine.
According to the relationship31 between Ere onset

and the LUMO energy, LUMO values of P1–P4

could be estimated as
(Ere onset
þ 4.4). Thus, the
LUMO values of P1–P4 were
(
1.80 þ 4.4)
Figure 6. Powder XRD patterns of P1 and P2. ¼
2.60 eV,
(
1.85 þ 4.4) ¼
2.55 eV,
(
1.75
þ 4.4) ¼
2.65 eV, and
(
1.77 þ 4.4) ¼
2.63
eV, respectively, indicating that the presence of
diazole units and electron-donating dialkoxyben-
an electron-donating

OCH3 unit in the triazine
zene units usually do not show PL in the solid
ring brought about the reduction of the LUMO
state because of the strong intermolecular
energy values of the polymers.
action.6(c) In our case, however, P1 and P2 with
an acceptor–donor system showed PL in the solid
state, and this suggested that the large triazine
unit likely restrained the intermolecular action.
Thermogravimetric analysis (TGA) showed
that P1–P4 had good thermal stability with a 5
wt % loss temperature of more than 360 8C under
N2, as shown in Figure 5 and Table 2.
The powder X-ray diffraction (XRD) patterns
of P1–P4 indicated that the polymers were semi-
crystalline, revealing that the polymers did not
form a well-packed structure because of the pres-
ence of a large triazine group in the polymers. As
an example, the XRD patterns of P1 and P2 are
shown in Figure 6.

Electrochemical Properties
Redox behaviors of P1–P4 were measured by CV
with their cast films on platinum wires. As shown
in Figure 7, the electrochemical reduction (or
n-doping) of P1 and P3 started at about
1.78 V
versus Agþ/Ag, whereas P2 and P4 showed the
onset
reduction onset potential (Ere ) at about
1.85
V. The reduction peaks of P1–P4 appeared at

2.07,
2.12,
2.08, and
2.11 V versus Agþ/Ag,
respectively, and the corresponding n-dedoping
peaks of P1–P4 appeared at
1.88,
1.88,
1.84,
and
1.88 V, respectively. The films of P1–P4
were stable under repeated CV scanning, giving Figure 7. CV charts of cast films of P1–P4 on Pt
almost the same CV curves; this suggested elec- wires (1 cm  1 cm) in an acetonitrile solution of 0.10 M
trochemical reversibility and stability of P1–P4 [Bu4N]BF4 with a sweep rate of 100 mV/s. I ¼ current;
from 0 to
2.5 V. E ¼ potential.
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola

The electrochemical oxidation (or p-doping) of
P1 and P2 started at about 0.95 V versus Agþ/Ag
and gave p-doping peaks at 1.09 and 1.08, respec-
tively, as can be seen in Figure 7. Unfortunately,
despite many efforts, the electrochemical oxida-
tion peaks of P3 and P4 were still hard to detect,
and this suggested that the oxidation of P3 and
P4 was out of the electrochemical window (0–1.5
V). Usually, the p-doping peak of polyfluorene
appears at about 1.25 V versus Agþ/Ag.34,35 Thus,
the electrochemical behavior of P3 and P4 under
oxidation was probably due to the strong elec-
tronic affinity of triazine. In contrast, the elec-
tron-donating alkyloxy groups in P1 and P2 may
have counteracted the effect of triazine. As a
result, P1 and P2 showed p-doping peaks.
CONCLUSIONS
A series of new p-conjugated poly(aryleneethynyl-
ene)s containing a 1,3,5-triazine unit in the main
chain were synthesized. The polymers, P1–P4,
showed good solubility in common organic sol-
vents and exhibited PL both in organic solvents
and in the solid state. All these polymers revealed
electrochemical stability and reversibility under
reduction. Investigations of these polymers are
expected to find polymers with better chemical
properties.
Financial support from the Science and Technology
Commission of Shanghai Municipality (05ZR14160),
the Chinese Academy of Sciences, and the Ministry of
Finance through the ‘‘Hundreds of Talents Project’’ is
acknowledged.
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