Macromolecules, Vol. 36, No. 11, 2003
Polyquinolines and Polyanthrazolines 3827
minescence studies were carried out by a Spex FL-2T2
spectrofluorimeter. The solutions of polymers for steady-state
PL studies were positioned such that the light emission was
detected at 90° from the incident beam. The PL quantum
efficiencies (φ) of polymers were estimated by using a solution
and refluxed for 4 h. After the methanol was evaporated at
reduced pressure, the aqueous residue was extracted with
ethyl acetate, and the extracts were washed with brine, dried
over Na
2 4
SO , and concentrated at reduced pressure to give 17.5
2
1
g (94.4%) of 2-acetylpyrrole, 3, mp 89-90 °C (lit. 89.5-90.5
-
7
1
Rhodamine B (1 × 10 mol/L, in m-cresol containing 0.2 wt
°C). H NMR (CDCl
6.93 (m, 1H, H-3), 6.25 (t, 1H, H-4), 2.42 (s, 3H, CH
2,5-Dia cetylp yr r ole (O) a n d 2,4-Dia cetylp yr r ole (M).
To a stirred mixture of 14.2 g (0.234 mol) of glacial acetic acid
and 37.8 g (0.390 mol) of trifluoroacetic anhydride under N
3
): δ 9.83 (br s, 1H, H-1), 7.05 (m, 1H, H-5),
%
di-m-cresyl phosphate (DCP)) as a standard (φPL ) 95%) and
3
CO).
1
0c
21
referring to the method in the literature.
Time-resolved
photoluminescence decay measurements were performed using
an Applied Photophysics SP-70 nanosecond spectrofluorimeter
based on the time-correlated single photon counting technique.
2
was added dropwise a solution of 17 g (0.156 mol) of 3 in 235
mL of dry benzene. The whole was stirred for 2 weeks at room
temperature during which the color turned from cranberry to
black. The mixture was poured into 160 mL of water contain-
ing 80 g (0.94 mol) of sodium bicarbonate, and the resulting
solution (pH is about 7) was extracted with ethyl acetate (6 ×
150 mL). Evaporation of the solvent from the dried (magne-
sium sulfate) extract left 24 g of black solid, which was
triturated with 3 × 40 mL of hot water for 2 h. The triturate
water was cooled and added 45 g of sodium chlorate and
extracted with ethyl acetate (6 × 150 mL). Removal of the
solvent from the dried extract gave 15.1 g of solid which was
chromatographed in a column of silica gum (100-200 mesh).
Elution with petroleum ether-diethyl ether (2:1) afforded
three products. The first eluted product was the starting 3 (5.5
g, 32.4%), mp 89-90 °C. The second eluted product was 2,5-
diacetylpyrrole O (3.81 g, 16.2%), mp 158-159 °C. Recrystal-
lization from water-ethanol and dry nitromethane afford
colorless needles, mp 160-160.5 °C (lit.21 159.5-160 °C). IR
The excitation source was a N
2
lamp which had a ∼3 ns pulse
width at a repetition rate of 50 kHz. The samples were excited
at 351 nm; the emission was collected at a 90° angle to the
excitation beam. The PL decay was detected at the PL emission
peak for each polymer. Alternating-current conductivities were
measured between a pair of stainless steel electrodes at
varying temperature using a Solortron 1255 impedance ana-
lyzer with the frequency range of 0.1 Hz-1 MHz and an
oscillating voltage of 10 mV.
Optical quality thin films of the polymers were obtained by
spin-coating onto silica substrates from their m-cresol (PAO,
PAM, PBO, PBM) or m-cresol containing 0.2 wt % DCP
solutions (PCO, PCM, PDO, PDM). The thin films were dried
overnight at 125 °C in a vacuum or placed in ethanol
containing 10 wt % triethylamine for 1-2 days and then dried
overnight at 60 °C in a vacuum.
The proton conducting membrane was cast from a 6.6 wt %
solution of polymer in DMAC containing 0.6 wt % LiCl as
stabilizing agent by drawing on glass plates, using spacers to
regulate its thickness. The cast solution was dried overnight
at 60-70 °C and then dried at 130 °C under vacuum for 10 h.
It was placed in boiling-water for 2-3 h to remove any traces
of lithium and residual organic solvent, before being immersed
(KBr): 3309 (NH s), 3108 (CH sh), 1662, 1648 (CH
3
CO), 1538,
): δ 9.91 (br s,
1H, H-1), 6.86 (d, 2H, H-3, H-4), and 2.49 (s, 6H, CH CO). Anal.
Calcd for C NO : C, 63.57; H, 6.00; N, 9.27. Found: C,
-
1
1
1427, 1360, and 1252 cm
. H NMR (CDCl
3
3
8
H
9
2
63.75; H, 5.94; N, 9.13. The third eluted product was 2,4-
diacetylpyrrole M (10.6 g, 45.1%), mp 137-138 °C. Two
recrystallizations from petroleum-THF, mp 139.5-140 °C
(lit.21 139.5-140 °C). IR (KBr): 3178 (NH s), 2981 (CH w),
in 6 mol/L H
membrane (200 µm) was washed with water and blotted with
filter paper. The absorption level of H PO in polymer/H PO
4
3 4
PO /water-ethanol (1:1.5) for 3-5 days. The
3
4
3
complex was determined by measuring the change in the mass
before and after the immersion.
1662, 1643 (CH
946, 935, and 843 cm . H NMR (CDCl
H-1), 7.62 (two overlapping d, 1H, H-5), 7.32 (d, 1H, H-3), 2.48
(s,3H, CH CO), and 2.47 (s, 3H, CH CO). Anal. Calcd for C
NO : C, 63.57; H, 6.00; N, 9.27. Found: C, 63.59; H, 6.03; N,
8.99.
P olym er Syn th esis. P oly(2,2′-(2,5-p yr r yl)-4,4′-(p,p′-oxy-
3
CO), 1556, 1497, 1440, 1381, 1284, 1217, 1156,
-
1 1
3
): δ 10.17 (br s, 1H,
Mon om er Syn t h esis. 4,4′-Bis(2-aminobenzoyl)diphenyl
2
ether (A), 4,6-dibenzoyl-1,3-phenylenediamine (C), and 2,5-
3
3
8 9
H -
dibenzoyl-1,4-phenylenediamine (D) were synthesized accord-
2
1
ing to the literature. 4,4′-Diamino-3,3′-dibenzoyldiphenyl
ether (B) was prepared from p-chloronitrobenzene as a raw
1
5
material by modifying a method reported.
1
d ip h en ylen e)bisqu in olin e), P AO. A solution of 6.64 g of di-
2
0
7a
-(p-Tolylsu lfon yl)p yr r ole, 1. To a vigorously stirred
m-cresyl phosphate (DCP) and 2.23 g of freshly distilled
solution of 43.6 mL (0.60 mol) of pyrrole and 400 mL of
absolute tetrahydrofuran at 25 °C was slowly added 20 g (0.50
mol) of metal potassium. The mixture was allowed to heat to
the reflux temperature and maintained at reflux until all of
the metal had reacted (about 3 h). The white slurry was diluted
with 350 mL of solvent, and a solution of 76.2 g (0.40 mol) of
p-tolylsulfonly chloride (TsCl) in 450 mL of tetrahydrofuran
was added dropwise over a period of 45 min. After the resulting
mixture had been stirred at room temperature overnight, it
was filtered to yield a solution which was evaporated to
dryness under reduced pressure; the solid residue was treated
with activated charcoal and recrystallized from methanol to
m-cresol was added to equimolar amounts (0.993 mmol) of both
A (0.405 g) and O (0.150 g) in a cylindrical-shaped reaction
flask fitted with a mechanical stirrer. The reactor was purged
with argon for 5-10 min before the temperature was raised
to 135-140 °C in about 30 min. As the viscosity of the reaction
mixture increased with time, small amounts of m-cresol were
added to the reaction mixture to facilitate efficient stirring.
The reaction was maintained at this temperature for 60 h
under static argon. After cooling, the resulting viscous solution
was added dropwise into an agitated solution of 450 mL of
ethanol containing 10% v/v of triethylamine. The precipitated
polymer was then chopped in a blender and collected by suction
filtration. The polymer was purified by continuous extraction
in a Soxhlet extractor for 24 h with a ethanol solution contain
15% v/v triethylamine and dried at 100 °C under vacuum for
24 h to afford 0.444 g (92%) of pure polymer PAO.
2
0
give 53.9 g (61.0%) of white crystals, mp 105-106 °C (lit.
04.5 °C).
-(p-Tolysu lfon yl)-2-a cetylp yr r ole, 2. To a solution of
acetic anhydride (27 g, 0.26 mol) in 720 mL of 1,2-dichloro-
ethane at 25 °C was added BF ‚OEt (75 g, 0.52 mol). The
1
1
3
2
IR (KBr): 3436 (ν(N-H)), 3060 (ν(C-H)), 1592 (ν(C-C)),
1543 (ν(C-N)), 1492 (ν(C-C)), 1424, 1393, 1348, 1231
(ν(C-O)), 1205, 1167, 1101, 1014, 835 (δ(C-H)), 761, 711, 595,
mixture was stirred for 10 min, 1-(p-tolysulfonyl)pyrrole (50
g, 0.23 mol) in 240 mL of 1,2-dichloroethane was added, and
the mixture was stirred at 25 °C for 2 h. The reaction was
quenched with cold water, and the residue remaining after
concentration at reduced pressure was recrystallized from
-
1
572 cm (δ(C-H)). Anal. Calcd: C, 83.76; H, 4.34; N, 8.62.
Found: C, 83.24; H, 4.18; N, 8.36.
P oly(2,2′-(2,4-pyr r yl)-4,4′-(p,p′-oxydiph en ylen e)bisqu in -
olin e), P AM. Equimolar amounts (0.961 mmol each) of A and
M were reacted in 6.41 g of DCP and 2.22 g of m-cresol with
a procedure similar to that described above to give a yield of
91%.
IR (KBr): 3428(M(N-H)), 3058(M(C-H)), 1592 (ν(C-C)),
1544 (ν(C-N)), 1491 (ν(C-C)), 1415, 1394, 1349, 1232
(ν(C-O)), 1199, 1166, 1098, 1014, 946, 834 (δ(C-H)), 760, 699,
chloroform-hexane (1:5) to afford 48.9 g of pure 2 (80.5%),
1
mp 110-111 °C. H NMR (CDCl
3
): δ 7.85-7.98 (m, 2H), 7.40-
7
1
.65 (m, 2H), 7.85 (dd, 1H, H-5), 7.05 (dd, 1H, H-3), 6.35 (t,
H, H-4), 2.35 (s, 3H, CH CO), and 2.44 (s, 3H, CH ).
-Acetylp yr r ole, 3. To a stirred solution of 45 g (0.17 mol)
3
3
2
of 2 in 300 mL of methanol was added dropwise 300 mL of 5
mol/L NaOH at room temperature. The solution was heated