(10 ml) was refluxed for 12 h. After cooling, water (20 ml) was
added and the mixture was extracted with dichloromethane.
The organic phase was dried with anhydrous sodium sulfate,
the solvent was removed in vacuo at 25 °C, and the residue
was recrystallized (MeOH). Yield, 0.14 g (21%), yellow needles;
mp 102–103 °C. IR (KBr): n˜/cm−1=1641, 1598, 1545, 1502,
1292, 1242, 832, 761, 752, 690; UV–VIS (CHCl ): l /nm
powder with a greenish lustre; mp 165–166 °C. IR (KBr):
n/cm−1=2922, 2851, 1639, 1608, 1536, 1513, 1283, 1241, 1210,
˜
1175, 816; UV–VIS (CHCl ): l /nm (log e)=278 (4.241),
3
max
448 (4.620); (CF CO H): l /nm (log e)=261 (4.352), 441
max
(4.731). Calc. for (C H N OΩ0.25 H O) [(485.2) ]: C, 81.69;
3
2
33 40
2
2
n
n
H, 8.41; N 5.77%. Found: C, 81.68; H, 8.31; N, 5.56%.
3
max
(log e)=251 (4.248), 398 (4.494), 445 (sh, 4.303); (HCO H):
2
Poly[3-amino-2-(p-dodecyloxyphenyl)prop-2-eniminyl(p-
phenylenevinylphenylene)] 7c
l
/nm (log e)=384 nm (5.084); 1H NMR (400 MHz,
max
CDCl ): d=3.83 (s, 3 H, OCH ), 6.92–7.37 (m, AA∞BB∞,
3
3
J 8.7 Hz, 14 H, phenyl-H, phenylene-H), 8.01 (s, br, 2 H,
NCHC); 13C NMR (100 MHz, CDCl ): d=55.41 (q, OCH ),
109.46 (s, C-2), 114.38, 118.33 (d, C-4), 127.85 (d, C-6), 129.45
As described for 7a with 5d (0.95 g, 2.00 mmol) and 4,4∞-
diaminostilbene (0.42 g, 2.00 mmol). Yield, 0.62 g (60%),
brown-red powder with a greenish lustre; mp 156–157 °C. IR
3
3
(d, C-5), 129.80, 133.11, 146.37 (s, C-3), 149.00 (d, C-1), 158.41.
(336.4): C, 79.44; H, 6.29;
(KBr): n/cm−1=2922, 2851, 1639, 1606, 1538, 1511, 1286, 1243,
˜
Calc. for C H N OΩ25 CH OH
N, 8.33%. Found: C, 79.35; H, 6.17; N 8.34%.
1177, 1027, 827; UV–VIS (CHCl ): l /nm (log e)=310
22 20
2
3
0.25
3
max
(4.260), 473 (4.620); (CF CO H): l /nm=296, 458. Calc. for
max
(C H N OΩ0.5 H O) [(515.7) ]: C, 81.52; H, 8.40; N, 5.43%.
Found; C, 81.66; H, 8.18; N 5.71%.
3
2
35 42
2
2
n
n
3-(p-Dimethylaminophenylamino)-2-(p-methoxyphenyl)-N-(p-
dimethylaminophenyl)prop-2-enimine 6f
A suspension of 5c30 (0.66 g, 1.98 mmol), N,N-dimethyl-p-
phenylenediamine (0.54 g, 3.96 mmol), and triethylamine
(0.78 ml, 5.38 mmol) in EtOH (10 ml) was refluxed for 12 h.
After cooling, water (20 ml) was added and the mixture was
extracted with dichloromethane. The organic phase was dried
over anhydrous sodium sulfate and the solvent was removed
in vacuo at 25 °C. The residue was dissolved in diethyl ether,
the solution filtered over silica gel, dried with anhydrous
magnesium sulfate and the solvent was evaporated at room
temperature. Yield, 0.12 g (14%), yellow brownish powder; mp
Poly[3-amino-2-(1-pyridinio)prop-2-eniminyl(p-phenylene)
tetrafluoroborate] 7d
The suspension of 5b30 (0.76 g, 2.01 mmol) and p-phenylenedi-
amine (0.22 g, 2.04 mmol) in a mixture of diglyme (18 ml) and
AcOH (2 ml) was heated to 120 °C for 3.5 h. After cooling, the
precipitate was suction filtered and washed with MeOH and
ether. Yield, 0.56 g (91%), dark red powder; mp 296 °C. IR
(KBr): n˜/cm−1=1646, 1516, 1301, 1084, 827, 774, 681, 520;
UV–VIS (DMSO): l /nm (log e)=256 (4.111), 453 (4.369).
max
147–148 °C. IR (KBr): n/cm−1=1636, 1608, 1542, 1512, 1293,
˜
Calc. for (C H BF N Ω0.4 H O) [(316.3) ]: C, 53.17; H,
4.08; N, 13.29%. Found: C, 53.36; H, 4.38; N, 13.10%.
14 12
4
3
2
n
n
847; UV–VIS (DMSO): l /nm (log e)=307 (4.396), 452
max
(4.436); (HCO H): l /nm (log e)=385 (4.763), 499 (3.123);
2
max
1H NMR (400 MHz, CDCl ): d=2.93 (s, 12 H, NCH ), 3.83
3
3
Poly[3-amino-2-(4-dimethylamino-1-pyridinio)prop-2-
eniminyl(p-phenylene) tetrafluoroborate] 7e
(s, 3 H, OCH ), 6.76–7.09 (AA∞BB∞, J 9.0 Hz, 8 H, phenylene-
3
H), 6.91–7.29 (AA∞BB∞, J 8.4 Hz, 4 H, phenylene-H), 7.93 (s, 2
H, NCHC); 13C NMR (100 MHz, CDCl ): d=41.15 (q, NCH ),
55.41 (q, OCH ), 108.10 (s, C-2), 113.92 (d, C-5), 114.15, 119.34
The suspension of 5e31 (0.84 g, 1.99 mmol) and p-phenylenedi-
amine (0.22 g, 2.04 mmol) in MeOH (20 ml) and AcOH (five
drops) was refluxed for 1 h. After cooling, the precipitate was
suction filtered (Schlenck funnel) and washed with acetic acid,
MeOH and ether. Yield, 0.54 g (71%), dark red powder; mp
280 °C (decomp.). IR (KBr): n˜/cm−1=1647, 1608, 1575, 1516,
1403, 1289, 1190, 1123, 1084, 825, 522; UV–VIS (DMSO):
3
3
3
(d, C-4), 127.22, 133.76, 137.27 (s, C-3), 147.39 (d, C-1), 147.75
(s, C-6), 157.64. Calc. for C H N O (414.6): C, 75.33; H, 7.29;
N, 13.52%. Found: C, 74.83; H, 7.26; N, 13.27%.
26 30
4
Poly[3-amino-2-(p-dodecyloxyphenyl)prop-2-eniminyl(p-
phenylene)] 7a
l
/nm (log e)=292 (4.361), 440 (4.439). Calc. for
max
(C H BF N Ω1.5 H O) [(379.2) ]: C, 50.68; H, 5.32; N,
14.78%. Found: C, 50.80; H, 5.07; N 15.73%.
The solution of 5d (2.85 g, 6.01 mmol), p-phenylenediamine
(0.66 g, 6.11 mmol), and five drops of AcOH in EtOH (15 ml)
was refluxed for 15 h. After cooling, the precipitate was col-
lected by suction filtration and washed with EtOH, then with
a 151 mixture of EtOH and triethylamine, and finally with
EtOH. After triturating with ether, the residue was collected
by filtration. Yield, 1.11 g (45%), dark red powder with a
greenish lustre; mp 199–200 °C. IR (KBr): n˜/cm−1=2924, 2853,
16 17
4
4
2
n
n
Poly{2,2∞-(4,4∞-bipyridine-1,1∞-diylium)di[3-aminoprop-2-
eniminyl(p-phenylene)] bis(tetrafluoroborate)} 7f
The suspension of 5f 31 (0.38 g, 0.50 mmol) and p-phenylenedi-
amine (0.12 g, 1.11 mmol) in MeOH (20 ml) and AcOH (five
drops) was refluxed for 9 h. After cooling, the precipitate was
suction filtered (Schlenck funnel) and washed with AcOH,
MeOH, a 151 mixture of MeOH and triethylamine, MeOH,
and ether. Yield, 0.28 g (100%), black powder; mp >350 °C.
IR (KBr): n˜/cm−1=1637, 1608, 1514, 1299, 1084, 833, 523.
Calc. for (C H B F N ΩC H N ΩCH OH) [(756.3) ]: C,
1637, 1606, 1538, 1508, 1279, 1243, 1027, 827; UV–VIS (CHCl ):
3
l
l
/nm (log e)=283 (4.210), 484 (4.210); (CF CO H):
max
max
3
2
/nm (log e)=465 (4.459). Calc. for (C H N OΩ0.5 H O)
[(413.6) ]: C, 78.41; H, 9.02; N, 6.77%. Found: C, 78.65; H,
27 36
2
2
n
n
8.89; N, 7.12%.
28 22 2 8
6
6
8
2
3
n
n
Poly[3-amino-2-(p-dodecyloxyphenyl)prop-2-eniminyl(p-
phenylphenylene)] 7b
55.58; H, 4.53; N, 14.82%. Found: C, 56.11; H, 4.67; N, 14.60%.
Triethylamine (0.30 ml, 2.07 mmol) and 5d (0.95 g, 2.00 mmol)
were added successively to a suspension of benzidine dihydro-
chloride (0.52 g, 2.02 mmol) in EtOH (10 ml). The mixture
was refluxed for 18 h. After cooling, the precipitate was suction
filtered and washed with EtOH, then with a 151 mixture of
EtOH and triethylamine, and finally with EtOH. The residue
was dissolved in chloroform and the solution was filtered. The
solvent was removed in vacuo at 50 °C, the residue was trituated
with ether and collected by filtration. Yield, 0.67 g (69%), red
Poly{2,2∞-(4,4∞-bipyridine-1,1∞-diylium)di[3-aminoprop-2-
eniminyl(p-phenylvinylphenylene)] bis(tetrafluoroborate)} 7g
As described for 10f with 8f31 (0.38 g, 0.50 mmol) and 4,4’-
diaminostilbene (0.22 g, 1.05 mmol). Yield, 0.35 g (77%), black
powder; mp >350 °C. IR (KBr): n˜/cm−1=1636, 1603, 1576,
1300, 1084, 1063, 964, 835, 522. Calc. for (C H B F N Ω0.5
44 34 2 8
6
CH OH) [(836.4) ]: C, 63.90; H, 4.34; N, 10.05%. Found: C,
64.15; H, 4.72; N, 12.00%.
3
n
n
2016
J. Mater. Chem., 1998, 8(9), 2011–2018