Supporting information for
Design of low crystalline isobutyl-substituted caged
silsesquioxane derivatives by star-shaped architectures
liked with aliphatic chains
Yuta Yasumoto, Shinichi Sakurai, Hiroaki Imoto, and Kensuke Naka
Heptaisobutylvinyl-T8-silsesquioxane (1a)
To a dried THF solution (100 mL) of heptaisobutyl-tricycloheptasiloxane trisodium silanolate
(1) (5.0 g, 6.3 mmol) and triethylamine (3,3 mL, 24 mmol) was added dropwise a THF solution
(5 mL) of trichlorovinylsilane (2) (0.88 mL, 7.0 mmol) in an ice bath and stirred for 1h at 0 ˚C
and 3 h at room temperature. After removing volatiles under reduced pressure to obtained a crude
product. The crude product was dissolved in minimal amount of ethyl acetate and poured in to
methanol to give a white solid in 43% yield. 1H-NMR(CDCl3): δ 0.61 (dd, 32H, -Si-CH2-), 0.94
(d, 84H, -Si-CH2-CH-CH3), 1.82-1.92 (m, 14H, -Si-CH2-CH-), 5.93-6.03 (m, 2H, -CH=CH2).
13
C-NMR(CDCl3): δ 22.59, 22.69, 24.04, 25.89, 130.12, 135.98.
-67.86, -68.58.
1
29
Si-NMR(CDCl3): δ -67.40,
Allylheptaisobutyl-T8-silsesquioxane (1b)
To a dried THF solution (120 mL) of heptaisobutyl-tricycloheptasiloxane trisodium silanolate
(5.0 g, 6.3 mmol) and triethylamine (4.4 mL, 32 mmol) was added dropwise a THF solution (5.0
mL) of trichlorooallylsilane (0.99 mL, 7.0 mmol) in an ice bath and stirred for 1h at 0 ˚C and 3 h
at room temperature. After removing volatiles under reduced pressure to obtained a crude
product. The crude product was dissolved in minimal amount of ethyl acetate and puried in to
methanol to give a white solid in 46% yield. 1H-NMR(CDCl3): δ 0.61 (dd, 32H, -Si-CH2-), 0.94
(d, 84H, -Si-CH2-CH-CH3), 1.82-1.92 (m, 14H, -Si-CH2-CH-), 5.93-6.03 (m, 2H, -CH=CH2).
13
C-NMR(CDCl3): δ 19.96, 22.60, 22.72, 24.06, 25.90, 114.98, 132.43.
29
Si-NMR(CDCl3): δ
-67.51, -67.90, -71.78.
Octakis[3-(heptaisobutyl-T8-silsesquioxy)
propyldimethylsiloxy]-Q8-silsesquioxane
(3b)
3b was prepared according to the previous our paper.1 Yield: 28%. 1H NMR (CDCl3, 400MHz): δ
0.12 (s, 48H, Si-CH3), 0.60 (m, 112H, Si–CH2–CH–(CH3)2), 0.67 (br, 32H, Si–CH2–CH2–CH2–
Si), 0.95 (d, J=6.6Hz, 336H, Si–CH2–CH–(CH3)2), 1.45 (br, 16H, Si–CH2–CH2–CH2–Si), 1.85
(m, 56H, Si–CH2–CH–(CH3)2). 13C NMR (CDCl3, 100MHz): δ 25.68, 23.87, 23.85, 22.51, 22.49,
21.32, 16.44, 16.23, -0.46.
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Si NMR (CDCl3, 80MHz): δ -109.07, -67.92, -67.77, 12.17.
MALDI-TOF-MS: calcd for [M+Na]+, 7901.348; obs, 7901.205.
1 H. Araki, K. Naka, Polym. J., 2012, 44, 340.
2
Heptaisobutyloctenyl-T8-silsesquioxane (1c)
(A)
c
a, d
b
j
i
k
(B)
Figure S1. (A) 1H- and (B) 13C-NMR spectra of 1c in CDCl3.
3
e, f,
g, h
C, D
A
B
D
C
B
Figure S2. 29Si-NMR spectrum of 1c in CDCl3.
4
Octakis[3-(heptaisobutyl-T8-silsesquioxy) ethyldimethylsiloxy]-Q8-silsesquioxane (3a)
(A)
c
a,
f
b
d, e
(B)
Figure S3. (A) 1H- and (B) 13C-NMR spectra of 3a in CDCl3.
5
C,(D
R
R
O
R
Si
R
O
Si
O
O
Si
O F
O
O
Si
B
R
R
O
Si
O
O
Si
O
Si
Si
O
A
R
iBu
R
R=
O
E
Si
A
iBu
O
Si
O
O
Si
Si
iBu
B
O
O
Si
O
O
O
Si
iBu
iBu
O
Si
O
O
Si
Si
O
D
C
iBu
iBu
F
E
Figure S4. 29Si-NMR spectrum of 3a in CDCl3.
6
Octakis[3-(heptaisobutyl-T8-silsesquioxy) octyldimethylsiloxy]-Q8-silsesquioxane (3c)
H2O
c
a, d, k
l
b
e-j
Figure S5. (A) 1H- and (B) 13C-NMR spectra of 3c in CDCl3.
7
C,(D
R
R
O
Si
O
R
O
Si
O
Si
R
B
Si
O F
O
O
Si
O
R
R
O
Si
O
O
Si
Si
O
A
R
R
iBu
R=
O
Si
E
A
O
Si
O
iBu
O
Si
Si
iBu
B
O
O
Si
O
O
O
Si
iBu
iBu
O
Si
O
O
Si
Si
O
D
iBu
C
iBu
F
E
Figure S6. 29Si-NMR spectrum of 3c in CDCl3.
8
Figure S7. TGAthermograms of 3a, 3b, and 3c at a heating rate of 10 ˚C/min in N2 flow.
9