Supporting Information for
Asymmetric Organic-Inorganic Hybrid Giant Molecule:
Cyanobiphenyl Mono-substituted Polyhedral Oligomeric
Silsesquioxane Nanoparticles for Vertical Alignment of
Liquid Crystals
Dae-Yoon Kim, Soeun Kim, Sang-A Lee, Young-Eun Choi, Won-Jin Yoon, Shiao-Wei Kuo,
Chih-Hao Hsu, Mingjun Huang, Seung Hee Lee,* and Kwang-Un Jeong*
Chemical structures and purities of POSS-CBP1 and its intermediates were confirmed by 1H
NMR in deuterated chloroform (CDCl3) and deuterated dimethyl sulfoxide (DMSO-d) at
room temperature. All the chemical compounds synthesized in this research were synthesized
in this research were purified by column chromatography using the silica gel. Chemical shifts
were quoted in part per million (ppm) with a reference of tetramethylsilane (TMS). Chemical
structure of compound 1 was confirmed by appearance of -CH2-CH3 at the end of the ester
groups (1.26 ppm, 3H). Chemical structure of compound 2 was confirmed from the
disappearance of ethyl group in ester and appearance of broad and intense single peak at 11.6
ppm corresponding to the carboxylic acid (-COOH). Chemical structure of POSS-CBP1 (3)
was confirmed by increased integration of protons and a new peak as -CONH- (5.44 ppm,
1H) corresponding to the POSS group.
To figure out the thermal stability of POSS-CBP1 molecules, thermogravimetric
analysis (TGA, Q-50, TA instrument) was employed. The scanning rate was 10 °C/min from
30 °C to 600 °C under nitrogen atmosphere. As shown in Figure S5, POSS-CBP1 began to
degrade at 304 °C from 5 % weight loss. Above 450 °C, POSS-CBP1 degraded completely.
This result may come from the outstanding thermal stability of POSS-CBP1 compound.
The thermal behavior of the phase transitions was studied using a Perkin-Elmer
PYRIS Diamond differential scanning calorimetry (DSC). For DSC experiments, the sample
weights were about 4.0 mg and the pan weights were kept constant with a precision of ±
0.001 mg. The temperature and heat flow scales were calibrated using standard materials at
10 °C/min. Transition temperatures were determined using the onset temperatures. Heating
experiments always preceded the cooling experiments in order to eliminate previous thermal
histories, and the cooling and heating rates were always kept identical at 10 °C/min. The
onset temperature was defined by the cross-point of the peak slope and the baseline in the
DSC trace. In cooling, the onset temperature was determined on the high-temperature side,
and upon heating the onset temperature determined was on the low temperature side. DSC
results of POSS-CBP1 showed only one peak both on cooling and on heating in Figure S6.
The onset temperature of the endothermic transition and corresponding heat are 156.1 °C and
45.4 kJ/mol. During the cooling, the onset transition temperature and heat are 127.5 °C and
41.2 kJ/mol. Although POSS-CBP1 molecules contain alkyl chain linker and cyanobiphenyl
(CB) as a mesogenic group, it doed not reveal liquid crystalline phase. The exothermic
transition of 41.2 kJ/mol should indicate the crystallization process of POSS-CBP1.
Figure S1. 1H NMR spectrum of compound 1.
Figure S2. 1H NMR spectrum of compound 2.
Figure S3. 1H NMR spectrum of compound POSS-CBP1 (3).
5 2 0 .9 1 6 7
[M-CBP1-R+K]+
90
80
70
1 1 6 5 .1 0 3 1
[M+H]+
60
50
with impurities
m/z 1203 (+K)
m/z 1165 (+H)
m/z 874 (-CBP1+H)
m/z 520 (-CBP1-R+K)
O
R
O
O
Si
Si
O
O
Si
O
Si
Si
O
R
O
R
O
40
N
H
O
R
Si
O
O
R
CBP1 (m/z 292)
O
Si
O
Si
R
R
R = i-butyl (m/z 57)
30
20
7 2 8 .8 2 4 4
5 7 1 .8 2 9 5
5 2 4 .9 2 0 1
10
8 7 8 .0 8 3 3
5 3 6 .9 0 8 9
5 5 5 .8 3 8 2
5 4 8 .8 6 2 5
500
7 6 3 .7 5 4 0
1 1 8 7 .0 6 1 0
[M+K]+
% Intensity
MALDI-TOF mass spectrum of POSS-CBP1
m/z 1164
8 7 4 .0 8 2 0
[M-CBP1+H]+
100
1 1 6 9 .1 0 6 9
1 2 0 3 .0 4 7 9
1 2 2 1 .0 2 3 3
1400
2 0 0 8 .0 9 2 9
2300
3200
Mass
(m/z)
Mass
Figure S4. MALDI-ToF MS spectrum of POSS-CBP1.
C
N
100
5% weight loss
at 304 °
C
60
40
20
0
0
100
200
300
400
500
600
Temperature (°
C)
Figure S5. TGA result of POSS-CBP1.
Endothermic
Weight (%)
80
heating at 10 °
C/min
cooling at 10 °
C/min
0
30
60
90
120 150 180 210 240
Temperature (°
C)
Figure S6. DSC thermograms of POSS-CBP1.