Macromolecules, Vol. 38, No. 20, 2005
Poly(diphenylacetylene) Membranes 8331
0.27 (s, 9H, SiCH3). 13C NMR (CDCl3, ppm): 162.4 (d, J ) 250
Hz, 1C, Ar), 141.1 (1C, Ar), 133.4 (d, J ) 8.2 Hz, 2C, Ar), 133.2
(2C, Ar), 130.6 (2C, Ar), 123.3 (1C, Ar), 119.3 (1C, Ar), 115.6
(d, J ) 22 Hz, 2C, Ar), 89.2 (1C, CtC), 88.6 (1C, CtC), -1.2
(3C, Si-C). Anal. Calcd for C17H17FSi: C, 76.1; H, 6.4. Found:
C, 75.9; H, 6.5.
Hz, 2C, Ar), 91.1 (1C, CtC), 86.6 (1C, CtC), 7.3 (3C,
SiCH2CH3), 3.3 (3C, SiCH2). Anal. Calcd for C20H21F3Si: C,
69.3; H, 6.1. Found: C, 69.6; H, 6.3.
1-(4-Tri-n-propylsilylphenyl)-2-(3,4,5-trifluorophenyl)-
acetylene (1g). This monomer was prepared by the same
method as for 1e using 4-(tri-n-propylsilyl)phenylacetylene
instead of 4-(trimethylsilyl)phenylacetylene. Yield 73%, liquid,
purity >99% (1H NMR). IR (KBr, cm-1): 2956, 1597, 1508,
1306, 1252, 1110, 855, 819, 760. 1H NMR (CDCl3, ppm): 7.46
(s, 4H, Ar), 7.13 (t, J ) 6.8 Hz, 2H, Ar), 1.34 (m, 6H,
SiCH2CH2), 0.96 (t, J ) 7.2 Hz, 9H, SiCH2CH2CH3), 0.79 (t, J
) 8.4 Hz, 6H, SiCH2). 13C NMR (CDCl3, ppm): 151.0 (ddd, 1J
1-(4-Trimethylsilylphenyl)-2-(2-fluorophenyl)acety-
lene (1b). This monomer was prepared by the same method
as for 1a using o-fluoroiodobenzene instead of p-fluoroiodo-
benzene. Yield 66%, colorless liquid. IR (KBr, cm-1): 2957,
1597, 1518, 1420, 1267, 1252, 1206, 1113, 1094, 951, 841, 820,
760. 1H NMR (CDCl3, ppm): 7.51 (m, 5H, Ar), 7.31 (t, J ) 9.2
Hz, 1H, Ar), 7.26-7.20 (br, 1H, Ar), 7.08 (q, J ) 9.2 Hz, 1H,
2
3
1
) 250 Hz, J ) 9.8 Hz, J ) 3.3 Hz, 2C, Ar), 141.2 (dt, J )
1
2
Ar), 0.27 (s, 9H, SiCH3). 13C NMR (CDCl3, ppm): 161.8 (d, J
250 Hz, J ) 16 Hz, 1C, Ar), 140.0 (1C, Ar), 134.0 (2C, Ar),
3
) 251 Hz, 1C, Ar), 141.4 (1C, Ar), 133.4 (1C, Ar), 133.2 (2C,
130.6 (2C, Ar), 122.1 (1C, Ar), 119.3 (t, J ) 5.0 Hz, 1C, Ar),
2
3
Ar), 130.7 (2C, Ar), 129.9 (1C, Ar), 123.9 (1C, Ar), 123.1 (1C,
115.9 (dd, J ) 16 Hz, J ) 6.6 Hz, 2C, Ar), 91.1 (1C, C≡C),
86.6 (1C, C≡C), 18.5 (3C, SiCH2CH2), 17.4 (3C, SiCH2CH2CH3),
15.1 (3C, SiCH2). Anal. Calcd for C23H27F3Si: C, 71.1; H, 7.0.
Found: C, 71.0; H, 7.1.
2
2
Ar), 115.4 (d, J ) 20.7 Hz, 1C, Ar), 111.9 (d, J ) 15.6 Hz,
1C, Ar), 94.6 (1C, CtC), 83.0 (1C, CtC), -1.2 (3C, SiC). Anal.
Calcd for C17H17FSi: C, 76.1; H, 6.4. Found: C, 76.1; H, 6.5.
1-(4-Trimethylsilylphenyl)-2-(3,4-difluorophenyl)acet-
ylene (1c). This monomer was prepared by the same method
as for 1a using 1-bromo-3,4-difluorobenzene instead of p-
fluoroiodobenzene. Yield 44%, white solid, mp 41.5-42.5 °C,
purity >99% (1H NMR). IR (KBr, cm-1): 2957, 1597, 1518,
1420, 1267, 1252, 1206, 1113, 1094, 951, 841, 820, 760. 1H
NMR (CDCl3, ppm): 7.52-7.44 (m, 4H, Ar), 7.31 (t, J ) 9.2
Hz, 1H, Ar), 7.26-7.20 (br, 1H, Ar), 7.08 (q, J ) 9.2 Hz, 1H,
Ar), 0.27 (s, 9H, SiCH3). 13C NMR (CDCl3, ppm): 150.5 (dd,
1-(4-Dimethylhexylsilylphenyl)-2-(3,4,5-trifluorophe-
nyl)acetylene (1h). This monomer was prepared by the same
method as for 1e using 4-(dimethylhexylsilyl)phenylacetylene
instead of 4-(trimethylsilyl)phenylacetylene. Yield 74%, liquid,
purity >99% (1H NMR). IR (KBr, cm-1): 2924, 1611, 1528,
1429, 1381, 1256, 1115, 1049, 857, 818, 783. 1H NMR (CDCl3,
ppm): 7.49 (d, J ) 8.0 Hz, 2H, Ar), 7.46 (d, J ) 8.0 Hz, 2H,
Ar), 7.14 (t, J ) 6.4 Hz, 2H, Ar), 1.32-1.21 (m, 8H, SiCH2-
(CH2)4CH3), 0.86 (t, J ) 6.4 Hz, 3H, SiCH2(CH2)4CH3), 0.74 (t,
J ) 6.8 Hz, 2H, SiCH2), 0.26 (s, 6H, SiCH3). 13C NMR (CDCl3,
2
1
2
1J ) 250 Hz, J ) 12 Hz, 1C, Ar), 150.0 (dd, J ) 250 Hz, J
) 12 Hz, 1C, Ar), 141.5 (1C, Ar), 133.2 (2C, Ar), 130.6 (2C,
Ar), 128.2 (d, 3J ) 6.6 Hz, 1C, Ar), 122.8 (1C, Ar), 120.4 (d, 2J
) 18 Hz, 1C, Ar), 120.1 (d, 3J ) 8.2 Hz, 1C, Ar), 117.4 (d, 2J )
17 Hz, 1C, Ar), 90.0 (1C, CtC), 87.5 (1C, CtC), -1.2 (3C, SiC).
Anal. Calcd for C17H16F2Si: C, 71.3; H, 5.6. Found: C, 71.7;
H, 5.8.
1
2
3
ppm): 151.0 (ddd, J ) 250 Hz, J ) 11 Hz, J ) 4.9 Hz, 2C,
1
2
Ar), 141.4 (1C, Ar), 140.2 (dt, J ) 250 Hz, J ) 16 Hz, 1C,
Ar), 133.5 (2C, Ar), 130.6 (2C, Ar), 122.3 (1C, Ar), 119.3 (t, 3J
) 5.0 Hz, 1C, Ar), 115.8 (dd, 2J ) 17 Hz, 3J ) 5.7 Hz, 2C, Ar),
91.1 (1C, CtC), 86.6 (1C, C≡C), 33.3 (1C, Si(CH2)5CH3), 31.6
(1C, Si(CH2)4CH2), 23.8 (1C, Si(CH2)3CH2), 22.6 (1C, Si-
(CH2)2CH2), 15.6 (1C, SiCH2CH2), 14.1 (1C, SiCH2), -3.1 (2C,
SiCH3). Anal. Calcd for C22H25F3Si: C, 70.6; H, 6.7. Found:
C, 70.8; H, 6.9.
1-(4-Trimethylsilylphenyl)-2-(3,5-difluorophenyl)acet-
ylene (1d). This monomer was prepared by the same method
as for 1a using 1-bromo-3,5-difluorobenzene instead of p-
fluoroiodobenzene. Yield 60%, white solid, mp 41.5-42.5 °C,
purity >99% (1H NMR). IR (KBr, cm-1): 2954, 1592, 1511,
1253, 1220, 1157, 1101, 837, 823, 758. 1H NMR (CDCl3, ppm):
7.51 (d, J ) 7.6 Hz, 2H, Ar), 7.48 (d, J ) 7.6 Hz, 2H, Ar) 7.04
(d, J ) 6.0 Hz, 2H, Ar), 6.79 (t, J ) 8.8 Hz, 1H, Ar), 0.28 (s,
1-Phenyl-2-(3,4-difluorophenyl)acetylene (1i). This mono-
mer was prepared by the same method as for 1c using
phenylacetylene instead of 4-(trimethylsilyl)phenylacetylene.
Yield 66%, white solid, mp 84.0-85.5 °C, purity >99% (1H
NMR). IR (KBr, cm-1): 3082, 1599, 1514, 1420, 1327, 1266,
1
1
9H, SiCH3). 13C NMR (CDCl3, ppm): 162.7 (dd, J ) 250 Hz,
1235, 1202, 1103, 951, 866, 754, 689. H NMR (CDCl3, ppm):
3J ) 13 Hz, 2C, Ar), 142.0 (1C, Ar), 133.3 (2C, Ar), 130.7 (2C,
7.48 (br, 2H, Ar), 7.35-7.35 (m, 4H, Ar), 7.08 (br, 1H, Ar), 7.04
(q, J ) 8.8 Hz, 1H, Ar). 13C NMR (CDCl3, ppm): 150.4 (dd, 1J
) 250 Hz, 2J ) 12 Hz, 1C, Ar), 149.9 (dd, 1J ) 250 Hz, 2J ) 13
Hz, 1C, Ar), 131.5 (2C, Ar), 128.5 (1C, Ar), 128.3 (2C, Ar), 128.1
Ar), 126.0 (t, 3J ) 12 Hz, 1C, Ar), 122.5 (1C, Ar), 114.4 (dd, 2J
4
2
) 19 Hz, J ) 7.4 Hz, 2C, Ar), 104.3 (t, J ) 25 Hz, 1C, Ar),
91.5 (1C, CtC), 87.4 (1C, CtC), -1.2 (3C, SiC). Anal. Calcd
for C17H16F2Si: C, 71.3; H, 5.6. Found: C, 71.3; H, 5.8.
1-(4-Trimethylsilylphenyl)-2-(3,4,5-trifluorophenyl)-
acetylene (1e). This monomer was prepared by the same
method as for 1a using 1-bromo-3,4,5-trifluorobenzene instead
of p-fluoroiodobenzene. Yield 63%, white solid, mp 49.0-50.0
°C, purity >99% (1H NMR). IR (KBr, cm-1): 2960, 1621, 1588,
2
2
(d, J ) 9.9 Hz, 1C, Ar), 122.5 (1C, Ar), 120.3 (d, J ) 18 Hz,
2
1C, Ar), 120.1 (d, J ) 7.4 Hz, 1C, Ar), 117.3 (d, J ) 17 Hz,
1C, Ar), 89.8 (1C, CtC), 87.2 (1C, CtC). Anal. Calcd for
C14H8F2: C, 78.5; H, 3.8. Found: C, 78.7; H, 3.8.
1-Phenyl-2-(3,5-difluorophenyl)acetylene (1j). This mono-
mer was prepared by the same method as for 1d using
phenylacetylene instead of 4-(trimethylsilyl)phenylacetylene.
Yield 71%, white solid, mp 41.5-42.5 °C, purity >99% (1H
NMR). IR (KBr, cm-1): 3085, 1641, 1589, 1496, 1425, 1352,
1
1425, 1358, 1123, 992, 842, 817, 764. H NMR (CDCl3, ppm):
7.51 (d, J ) 8.0 Hz, 2H, Ar), 7.47 (d, J ) 7.6 Hz, 2H, Ar), 7.14
(d, J ) 7.2 Hz, 2H, Ar), 0.28 (s, 9H, SiCH3). 13C NMR (CDCl3,
ppm): 151.0 (ddd, 1J ) 250 Hz, 2J ) 9.9 Hz, 3J ) 4.1 Hz, 2C,
1
1236, 1122, 987, 970, 855, 752. H NMR (CDCl3, ppm): 7.51
1
2
Ar), 142.0 (1C, Ar), 140.2 (dt, J ) 250 Hz, J ) 16 Hz, 1C,
Ar), 133.2 (2C, Ar), 130.7 (2C, Ar), 122.3 (1C, Ar), 119.3 (m,
1C, Ar), 115.8 (dd, 2J ) 16 Hz, 3J ) 5.8 Hz, 2C, Ar), 91.1 (1C,
CtC), 86.6 (1C, CtC), -1.3 (3C, SiC). Anal. Calcd for C17H15F3-
Si: C, 67.1; H, 5.0. Found: C, 66.8; H, 4.9.
(m, 2H, Ar), 7.36 (m, 3H, Ar), 7.03 (d, J ) 6.0 Hz, 2H, Ar),
6.79 (t, J ) 8.8 Hz, 1H, Ar). 13C NMR (CDCl3, ppm): 162.7
1
2
(dd, J ) 250 Hz, J ) 13 Hz, 2C, Ar), 131.7 (2C, Ar), 128.9
(1C, Ar), 128.4 (2C, Ar), 125.9 (1C, Ar), 122.2 (1C, Ar), 114.4
(d, 2J ) 19 Hz, 2C, Ar), 104.3 (t, 2J ) 25 Hz, 1C, Ar), 91.2 (1C,
CtC), 87.1 (1C, CtC). Anal. Calcd for C14H8F2: C, 78.5; H,
3.8. Found: C, 78.7; H, 3.8.
1-(4-Triethylsilylphenyl)-2-(3,4,5-trifluorophenyl)acet-
ylene (1f). This monomer was prepared by the same method
as for 1e using 4-(triethylsilyl)phenylacetylene instead of
4-(trimethylsilyl)phenylacetylene. Yield 78%, liquid, purity
>99% (1H NMR). IR (KBr, cm-1): 2956, 1610, 1529, 1429,
1379, 1256, 1115, 1049, 1008, 857, 808. 1H NMR (CDCl3,
ppm): 7.47 (s, 4H, Ar), 7.11 (t, J ) 6.8 Hz, 2H, Ar), 0.96 (t, J
1-Phenyl-2-(3,4,5-trifluorophenyl)acetylene (1k). This
monomer was prepared by the same method as for 1e using
phenylacetylene instead of 4-(trimethylsilyl)phenylacetylene.
Yield 65%, white solid, mp 95.5-96.5 °C, purity >99% (1H
NMR). IR (KBr, cm-1): 3078, 1611, 1586, 1428, 1380, 1257,
) 7.6 Hz, 9H, SiCH2CH3), 0.80 (q, J ) 7.6 Hz, 6H, SiCH2). 13
3
C
1208, 1045, 979, 858, 757. H NMR (CDCl3, ppm): 7.50 (d, J
1
1
2
NMR (CDCl3, ppm): 151.0 (ddd, J ) 250 Hz, J ) 11 Hz, J
) 4.1 Hz, 2C, Ar), 140.2 (dt, 1J ) 250 Hz, 2J ) 16 Hz, 1C, Ar),
139.2 (1C, Ar), 134.1 (2C, Ar), 130.6 (2C, Ar), 122.2 (1C, Ar),
) 3.2 Hz, 2H, Ar), 7.36 (m, 3H, Ar), 7.13 (t, J ) 7.2 Hz, 2H,
1
2
Ar). 13C NMR (CDCl3, ppm): 150.9 (ddd, J ) 250 Hz, J )
3
1
2
9.9 Hz, J ) 4.9 Hz, 2C, Ar), 140.2 (dt, J ) 250 Hz, J ) 16
Hz, 1C, Ar),131.6 (2C, Ar), 128.9 (1C, Ar), 128.4 (2C, Ar), 122.1
3
2
3
119.3 (t, J ) 5.0 Hz, 1C, Ar), 115.8 (dd, J ) 17 Hz, J ) 5.8