6428 Okumura et al.
Macromolecules, Vol. 36, No. 17, 2003
F igu r e 14. Proposed structures of γ-CD-PSicyc6 inclusion complex.
24H, methyl H of PS). FT-IR (KBr, cm-1): 3378 (νs, OH), 2934
(νs, CH), 1246 (νas, Si-C), 1157, 1080, 1030 (νs, CO), 840 (νs,
834 (νs, Si-C). Anal. Calcd for (C48H80O40)2.3(C34H102O15Si16) -
1.0
(H2O)22: C, 40.69; H, 7.16. Found: C, 40.68; H, 7.08.
1
Si-C). Anal. Calcd for (C42H70O35)2.3(C12H36O4Si5)1.0(H2O)16: C,
γ-CD-P Si550. Yield: 163 mg, 64%. H NMR (pyridine-d5,
400 MHz): δ 5.49 (d, 8H, C1H of γ-CD), 4.38 (t, 8H, C3H of
γ-CD), 4.17 (m, 24H, C5H and C6H of γ-CD), 4.03 (m, 8H, C2H
of γ-CD), 3.95 (t, 8H, C4H of γ-CD), 0.349, 0.308, 0.210 (m,
60H, methyl H of PS). FT-IR (KBr, cm-1): 3398 (νs, OH), 2940
(νs, CH), 1249 (νas, Si-C), 1158, 1081, 1025 (νs, CO), 760 (νs,
40.45; H, 7.08. Found: C, 40.90; H, 7.07.
1
â-CD-P Si320. Yield: 8.5 mg, 2.6%. H NMR (pyridine-d5,
270 MHz): δ 5.69 (d, 7H, C1H of â-CD), 4.79 (t, 7H, C3H of
â-CD), 4.54 (m, 21H, C5H and C6H of â-CD), 4.30 (m, 7H, C2H
of â-CD), 4.15 (m, 7H, C4H of â-CD), 0.155, 0.143 (m, 36H,
methyl H of PS). FT-IR (KBr, cm-1): 3397 (νs, OH), 2928 (νs,
CH), 1247 (νas, Si-C), 1028 (νs, CO), 841 (νs, Si-C). Anal. Calcd
Si-C). Anal. Calcd for (C48H80O40)3.0(C52H156O24Si25)1.0(H2O)12:
C, 41.83; H, 7.10. Found: C, 41.81; H, 7.22.
for (C42H70O35
)2.8(C8H24O2Si3)1.0(H2O)24: C, 39.67; H, 7.17.
1
γ-CD-P Si610. Yield: 141 mg, 58%. H NMR (pyridine-d5,
400 MHz): δ 5.49 (d, 8H, C1H of γ-CD), 4.38 (t, 8H, C3H of
γ-CD), 4.17 (m, 24H, C5H and C6H of γ-CD), 4.04 (m, 8H, C2H
of γ-CD), 3.96 (t, 8H, C4H of γ-CD), 0.355, 0.301, 0.211 (m,
66H, methyl H of PS). FT-IR (KBr, cm-1): 3407 (νs, O-H),
2927 (νs, C-H), 1249 (νas, Si-C), 1159, 1081, 1026 (νs, C-O),
Found: C, 39.69; H, 7.17.
P r ep a r a tion of γ-CD-P S In clu sion Com p lexes. PSi (Si
monomer unit: 5.0 × 10-4 mol) was put into a tube. An
aqueous solution of γ-CD (5.59 mL) containing 649 mg of γ-CD
(5.00 × 10-4 mol) was added at room temperature. The mixture
was supersonically agitated for about 15 min and then allowed
to stand overnight at room temperature. The precipitated
product was collected by centrifugation, dried under vacuum,
then washed with THF and dried under vacuum, and washed
with water and dried under vacuum to give the γ-CD-PSi
complex. The results are summarized in Table 1.
796 (νs, Si-C). Anal. Calcd for (C48H80O40)3.3(C52H156O24Si25) -
1.0
(H2O)20: C, 41.32; H, 7.11. Found: C, 41.32; H, 7.16.
1
γ-CD-P Si670. Yield: 198 mg, 87%. H NMR (pyridine-d5-
chloroform-d 2:1 v/v, 400 MHz): δ 5.48 (d, 8H, C1H of γ-CD),
4.38 (t, 8H, C3H of γ-CD), 4.17 (m, 24H, C5H and C6H of γ-CD),
4.15 (m, 8H, C2H of γ-CD), 3.95 (t, 8H, C4H of γ-CD), 0.349,
0.241, 0.210 (m, 72H, methyl H of PS). FT-IR (KBr, cm-1):
3388 (νs, O-H), 2941 (νs, C-H), 1248 (νas, Si-C), 1158, 1028
1
γ-CD-P Si90. Yield: 29.8 mg, 2.7%. H NMR (pyridine-d5,
270 MHz): δ 5.72 (d, 8H, C1H of γ-CD), 4.64 (t, 8H, C3H of
γ-CD), 4.38 (m, 18H, C5H and C6H of γ-CD), 4.28 (m, 8H, C2H
of γ-CD), 4.09 (m, 8H, C4H of γ-CD), -0.012 (s, 12H, methyl
H of PS). FT-IR (KBr, cm-1): 3399 (νs, O-H), 2929 (νs, C-H),
1248 (νas, Si-C), 1157, 1080, 1027 (νs, C-O), 862 (νs, Si-C).
(νs, C-O), 759 (νs, Si-C). Anal. Calcd for (C48H80O40
) -
3.7
(C52H156O24Si25
H, 7.06.
)1.0(H2O)18: C, 41.80; H, 7.02. Found: C, 41.79;
γ-CD-P Si780. Yield: 79.1 mg, 57%. 1H NMR (pyridine-d5-
benzene-d6 3:1 v/v, 400 MHz): δ 5.72 (d, 8H, C1H of γ-CD),
4.64 (t, 8H, C3H of γ-CD), 4.39 (m, 24H, C5H and C6H of γ-CD),
4.26 (m, 8H, C2H of γ-CD), 4.08 (t, 8H, C4H of γ-CD), 0.458,
0.429, 0.319, 0.244 (m, 84H, methyl H of PS). FT-IR (KBr,
cm-1): 3410 (νs, O-H), 2950 (νs, C-H), 1261 (νas, Si-C), 1158,
1080, 1027 (νs, C-O), 757 (νs, Si-C). Anal. Calcd for
Anal. Calcd for (C48H80O40
)1.6(C6H18OSi2)1.0(H2O)5.8: C, 42.79;
H, 6.69. Found: C, 42.78; H, 6.78.
1
γ-CD-P Si150. Yield: 279 mg, 64%. H NMR (pyridine-d5,
400 MHz): δ 5.72 (d, 8H, C1H of γ-CD), 4.63 (t, 8H, C3H of
γ-CD), 4.37 (m, 18H, C5H and C6H of γ-CD), 4.27 (m, 8H, C2H
of γ-CD), 4.09 (t, 8H, C4H of γ-CD), 0.079 (s, 18H, methyl H of
PS). FT-IR (KBr, cm-1): 3389 (νs, O-H), 2931 (νs, C-H), 1246
(νas, Si-C), 1158, 1081, 1036 (νs, C-O), 837 (νs, Si-C). Anal.
(C48H80O40
)4.3(C52H156O24Si25)1.0(H2O)21: C, 39.79; H, 7.61.
Found: C, 39.79; H, 7.61.
Calcd for (C48H80O40
)1.2(C8H24O2Si3)1.0(H2O)4.5: C, 42.66; H,
γ-CD-P Si960. Yield: 22.2 mg, 8.9%. 1H NMR (pyridine-
d5, 400 MHz): δ 5.72 (d, 8H, C1H of γ-CD), 4.64 (t, 8H, C3H of
γ-CD), 4.38 (m, 24H, C5H and C6H of γ-CD), 4.28 (m, 8H, C2H
of γ-CD), 4.09 (t, 8H, C4H of γ-CD), 0.381, 0.347, 0.229, 0.198
(m, 102H, methyl H of PS). FT-IR (KBr, cm-1): 3386 (νs, O-H),
2949 (νs, C-H), 1248 (νas, Si-C), 1158, 1080, 1028 (νs, C-O),
6.93. Found: C, 42.72; H, 7.11.
1
γ-CD-P Si200. Yield: 298 mg, 73%. H NMR (pyridine-d5,
400 MHz): δ 5.72 (d, 8H, C1H of γ-CD), 4.63 (t, 8H, C3H of
γ-CD), 4.39 (m, 24H, C5H and C6H of γ-CD), 4.27 (m, 8H, C2H
of γ-CD), 4.09 (t, 8H, C4H of γ-CD), 0.181, 0.148, 0.122 (m,
24H, methyl H of PS). FT-IR (KBr, cm-1): 3388 νs, O-H), 2939
νs, C-H), 1246 νas, Si-C), 1158, 1080, 1026 νs, C-O), 837 νs,
746 (νs, Si-C). Anal. Calcd for (C48H80O40
)2.0(C52H156O24Si25) -
1.0
(H2O)19: C, 40.07; H, 7.76. Found: C, 40.02; H, 8.36.
Si-C). Anal. Calcd for (C48H80O40)1.4(C12H36O4Si3)1.0(H2O)5.8: C,
42.51; H, 7.02. Found: C, 42.51; H, 7.18.
P r ep a r a tion of Dod eca m eth ylcycloh exa sila n e (P Si-
cyc6). Dodecamethylcyclohexasilane (PSicyc6) was prepared
starting from dimethyldichlorosilane by Wurtz-type reductive
oligomerization using an excess amount of lithium. PSicyc6
was purified by sublimation at 100 °C in vacuo and recrys-
tallization twice from n-hexane/ethanol. Characterization of
PSicyc6 was carried out by 1H/13C/29Si NMR and ultraviolet
absorption spectroscopy.
P r ep a r a tion of γ-CD-P Sicyc6 In clu sion Com p lex. PSi-
cyc6 179 mg (5.13 × 10-3 mol) was put into a tube. An aqueous
solution of γ-CD (5.59 mL) containing 649 mg of γ-CD (5.00 ×
10-4 mol) was added at room temperature. The mixture was
stirred vigorously for a week and then allowed to stand
overnight at room temperature. The precipitated product was
collected by centrifugation, dried under vacuum, then washed
γ-CD-P Si320. Yield: 57.8 mg, 27%. 1H NMR (pyridine-d5,
270 MHz): δ 5.72 (d, 8H, C1H of γ-CD), 4.63 (t, 8H, C3H of
γ-CD), 4.39 (m, 24H, C5H and C6H of γ-CD), 4.27 (m, 8H, C2H
of γ-CD), 4.10 (t, 8H, C4H of γ-CD), 0.330, 0.250, 0.167 (m,
36H, methyl H of PS). FT-IR (KBr, cm-1): 3375 (νs, O-H),
2939 (νs, C-H), 1247 (νas, Si-C), 1157, 1080, 1025 (νs, C-O),
837 (νs, Si-C). Anal. Calcd for (C48H80O40
)1.3(C22H66O9Si10) -
1.0
(H2O)9.9: C, 41.06; H, 7.39. Found: C, 41.07; H, 7.19.
1
γ-CD-P Si440. Yield: 141 mg, 59%. H NMR (pyridine-d5,
270 MHz): δ 5.72 (d, 8H, C1H of γ-CD), 4.63 (t, 8H, C3H of
γ-CD), 4.38 (m, 24H, C5H and C6H of γ-CD), 4.27 (m, 8H, C2H
of γ-CD), 4.09 (t, 8H, C4H of γ-CD), 0.345, 0.295, 0.178 (m,
48H, methyl H of PS). FT-IR (KBr, cm-1): 3377 (νs, O-H),
2944 (νs, C-H), 1248 (νas, Si-C), 1159, 1081, 1027 (νs, C-O),