1
Electronic Supplementary Information (ESI)
Photo and electrically switchable behavior of azobenzene containing pendant
bent-core liquid crystalline polymers
M.Vijay Srinivasan1, P. Kannan1∗, A. Roy2
1. Department of Chemistry, Anna University, Chennai, India;
2. Soft Condensed Matter, Raman Research Institute, Bangalore, India
SYNTHESIS
Synthesis of precursors
Synthesis of 4-(4'-(12-hydroxy-1-dodecyloxy)phenylazo)phenyl)acetamide (2)
The synthesis of 4-(4'-(12-hydroxy-1-dodecyloxy)phenylazo)phenyl)acetamide was
carried out by suspending (4-(4'-hydroxyphenylazo)phenyl)acetamide (0.01 mol), anhydrous
K2CO3 (0.02 mol), pinch of KI in dry DMF (80 mL) and the reaction mixture was refluxed with
constant stirring. Then 1-bromo-12dodecanol (0. 01 mol) added dropwise to the reaction mixture
and refluxed for 24 h. After completion of the reaction, the mixture was filtered and washed with
excess of DMF. The filtrate was poured in to ice water and extracted using diethyl ether, dried
with anhydrous sodium sulphate. An orange colored solid was obtained after removal of solvent
under vacuum, then product was purified by column chromatography (silica gel, chloroform)
(Yield: 75 %).
2: C26H37N3O3: FT-IR (KBr pellet, cm-1); 3328, 3065, 2932, 2851, 1667, 1585,
1411,1250, 1200, 1151, 852.1H-NMR (CDCl3, 400 MHz) δ (ppm): 8.20 (d, 1H, Ar-H), 7.83-7.76
(m, 4H, -Ar-H), 7.21-7.11 (m, 3H, -Ar-H), 4.0 (m, 2H, -CH2-CO-), 3.65 (t, 1H, -OH), 3.5 (t, 2H,
-CH2-OH), 2.01 (t, 3H, -CO-CH3), 1.73 (d, 2H, -CH2-), 1.52-1.41 (t, 6H, -CH2-), 1.29 (dd, 12H, -
2
CH2-).
C NMR (CDCl3, 400 MHz) δ (ppm): 168.5, 161.0, 150.6, 148.5, 143.2, 140.1, 123.4,
13
119.7, 68.1, 31, 29.1, 26.8 and 24.
Synthesis of 4-(4'-12-hydroxy-1-dodecyloxyphenylazo)aniline (3)
The synthesis of 4-(4'-12-hydroxy-1-dodecyloxyphenylazo)aniline (3) was carried out by
the hydrolysis of (4-(4'(12-hydroxy-1-dodecyloxy)phenylazo)phenyl)acetamide (0.05 mol) in
ethanol (100 mL) and 3N HCl (0.1 mol) and then the reaction mixture was refluxed for 4 h. After
completion of the reaction, the mixture poured into water (500 mL) and neutralized with
saturated NaHCO3 solution and extracted using chloroform, dried with sodium sulphate. The
crude product was recrystallized from ethanol to obtained dark brown color 4-(4'-12-hydroxy-1dodecyloxyphenylazo) aniline (Yield: 95 %).
3: C24H35N3O2: FT-IR (KBr pellet, cm-1); 3448, 3325, 3055, 2927, 2851, 1615, 1551,
1411,1251,1151, 834.1H-NMR (CDCl3, 400 MHz) δ (ppm): 8.45 (d, 2H, Ar-H), 7.83 (m, 2H, Ar-H), 7.18-6.83 (m, 4H, -Ar-H), 4.03 (m, 2H, -CH2-CO-), 3.62 (t, 1H, -OH), 3.51 (t, 2H, -CH2OH), 1.74 (d, 2H, -CH2-), 1.53-1.41 (t, 6H, -CH2-), 1.29 (dd, 12H, -CH2-).
13
C NMR (CDCl3,
400 MHz) δ (ppm): 161.2, 152.2, 143.2, 140.1, 125.4, 123.6, 114.0, 113.2, 68.2, 62.3, 31.5, 26.3
and 25.1.
Synthesis
of
3-(4-(4-(dodecyloxy)benzoyloxy)benzoyloxy)phenyl
4-((E)-(4-((E)-(4-(12-
hydroxydodecyloxy)phenyl)diazenyl)phenylimino)methyl)benzoate (10)
A typical procedure for the synthesis of 10 is as follows: 4-(4'-(12-hydroxy-1dodecyloxy)phenylazo)aniline
benzoyloxy)phenyl
(0.007
mol)
and
3-(4-(4-(12-dodecyloxy)
benzoyloxy)
4-formylbenzoate (0.007 mol) was dissolved in ethanol (50 mL) then
reaction mixture refluxed until yellow color precipitate thrown out. After completion of reaction,
3
the desired product was filtered out and washed with ethanol, then the product recrystallized
from ethanol to get yellowish brown powder (Yield: 75%).
10: C64H75N3O9: FT-IR (KBr pellet, cm-1); 3434, 3086, 2920, 2852, 2344, 1733, 1603,
1507, 1401, 1282, 1253, 1199, 1136, 1074, 839.;1H NMR (CDCl3, 400 MHz) δ (ppm): 8.65 (s,
H, -CH=N-), 8.39-8.28 (m, 4H, Ar-H), 8.11 (m, 2H, Ar-H),7.96-7.89 (m, 4H, -Ar-H), 7.85-7.46
(m, 6H, -Ar-H), 7.24 (m, 2H,-Ar-H), 7.18-7.12 (m, 4H, -Ar-H), 6.84 (m, 2H, -Ar-H), 4.01 (m,
4H, -OCH2-), 3.62 (t, 1H, -OH), 3.51 (m, 2H, -CH2-OH), 1.78 (d, 4H, -CH2-), 1.51-1.41 (m, 8H,
-CH2-), 1.31-1.26 (dd, 28H, -CH2-), 0.89 (m, 3H, -CH3). 13C NMR (CDCl3, 400 MHz) δ (ppm):
165.2, 161.3, 160.2, 153.6, 151.4, 147.2, 144.2, 130.7, 130.2, 129.7, 121.8, 121.4, 118.7, 115.9,
68.5, 62.8, 32.1, 26.3, 25.8 and 14.3.
Synthesis of 4-((3-formylphenoxy)carbonyl)phenyl 4-12-dodecyloxybenzoate (13)
To
a
mixture
of
4-(4'-12-dodecyloxybenzoyloxy)
benzoic
acid
(0.01
mol),
3-hydroxybenzaldehyde (0.01mol), dicyclohexylcarbodiimide (DCC) (0.012 mol), a catalytic
amount of 4-dimethylaminopyridine (DMAP) in dry dichloromethane (50 ml) was added and
stirred for 12 h. After completion of reaction, the precipitated N, N′-9-dicyclohexylurea was
filtered, washed with excess of dichloromethane and filtrate concentrated. The residue was
purified by silica gel column using chloroform as eluent. (Yield: 85%).
13: C27H26O6: FT-IR (KBr pellet, cm-1): 2916, 2851, 1736, 1603, 1262. 1H NMR (CDCl3,
400 MHz) δ (ppm): 9.77(s, 1H, -CHO), 8.20-8.06 (dd, 4H, Ar-H), 7.73(m, 4H, Ar-H), 7.52-43
(m, 2H, Ar-H), 7.30-6.9 (m, 4H, Ar-H), 3.79 (t, 2H, -OCH2), 1.79 (m, 2H, -CH2-), 1.33-1.29 (m,
6H, -CH2-), 0.91(t, 3H, -CH3).
13
C NMR (CDCl3, 400 MHz) δ (ppm): 191.0, 165.2, 162.7,
156.5, 151.9, 137.2, 130.7, 130.2, 127.6, 122.4, 114.6, 68.4, 31.9, 29.8, 22.5 and 14.4.
4
Synthesis
of
4-((3-((E)-(4-((E)-(4-(12-hydroxydodecyloxy)phenyl)
diazenyl)
phenylimino)methyl)phenoxy)carbonyl)phenyl 4-(dodecyloxy) benzoate (14)
4-(4'-(12-Hydroxy-1-dodecyloxy)phenylazo)aniline
(0.007
mol)
and
4-((3-
formylphenoxy)carbonyl)phenyl 4-(dodecyloxy)benzoate (0.007 mol) was dissolved in ethanol
(50 mL), then reaction mixture refluxed until yellow color precipitate thrown out. After
completion of reaction, the desired product was filtered out and washed with ethanol, then the
product recrystallized from ethanol to get yellowish brown powder (Yield: 75%).
14: C57H71N3O7: FT-IR (KBr pellet, cm-1); 3367, 3077, 2919, 2850, 2342, 1733, 1602,
1473, 1401, 1252, 1200, 1162, 1061, 845.;1H NMR (CDCl3, 400 MHz), δ (ppm): 8.49 (s, H, CH=N-), 8. 32 (m, 2H, Ar-H), 8.04 -7.94 (m, 4H, Ar-H), 7.85 (m, 2H, Ar-H), 7. 45- 7.41 (m, 4H,
Ar-H), 7.31 -7.20 (m, 4H, Ar-H),7.11 – 7.04 (m, 4H, Ar-H), 4.01- 3.97 (m, 4H, -OCH2-), 3.61 (t,
1H, -OH), 3.56 (m, 2H, -CH2-OH), 1.81 -1.72 (m, 4H, -CH2-), 1.54 -1.43 (m, 4H, -CH2-), 1.31.26 (m, 32H, -CH2-), 0.89 (m, 3H, -CH3). 13C NMR (CDCl3, 400 MHz) δ (ppm): 166.1, 165.1,
163.2, 161.4, 153.9, 151.1, 150.6 (s), 146.3, 138. 1, 132.2, 131.5, 130.6, 128.1, 127.2, 124.2,
123.3, 121.4, 120.1, 115.1, 114.2, 6.8, 62.4, 32.6, 31.3, 29.5 , 28.1, 26.7, 22.1 and 14.0.
Synthesis of 3-formylphenyl 4'-12-dodecyloxybiphenyl-4-carboxylate (20)
A
mixture
of
4'-12-dodecyloxybiphenyl-4-carboxylic
acid
(0.04
mol),
3-
hydroxybenzaldehyde (0.4 mol), DCC (0.4 mol), 5% wt. of DMAP catalyst were dissolved in
dichloromethane (200 mL) and the resulting mixture stirred for 12 h at room temperature under
nitrogen atmosphere. After completion of reaction, the precipitated byproduct urea was filtered
out, then the filtrate evaporated and product purified by silica gel column using chloroform as
5
eluent. After recrystallization in ethanol, 3-formylphenyl 4'-6-hexyloxybiphenyl-4-carboxylate
(Yield: 95%) was obtained as a white color powder.
20: C26H26O4; FT-IR (KBr pellet, cm-1); 2992, 2921, 1772, 1727, 1603, 1467, 1399,
1274, 1234. 1H NMR (CDCl3, 400 MHz) δ (ppm): 9.86 (m, 1H, -Ar-CHO), 8.24 (m, 2H, -Ar-H),
7.77-7.63 (m, 4H, -Ar-H), 7.43-7.33 (m, 4H, -Ar-H), 6.86 (m, 2H, -Ar-H), 3.96 (m, 2H, -OCH2), 1.71 (d, 2H, -CH2-),1.31-1.27 (dd, 4H, -CH2-), 0.98 (m, 3H, -CH3).
13
C NMR (CDCl3, 400
MHz) δ (ppm): 190.9, 165.1, 156.4, 151.8, 141.7, 137.1, 130.4, 129.8, 128.4, 127.4, 114.1, 68.2,
31.9, 29.7, 25.7 and 14.1.
Synthesis
of
3-((E)-(4-((E)-(4-(12-hydroxydodecyloxy)
phenyl)
diazenyl)
phenylimino)methyl)phenyl 4'-(dodecyloxy)biphenyl-4-carboxylate (21)
4-(4'-(12-hydroxy-1-dodecyloxy)phenylazo)aniline (0.007 mol) and 3-formylphenyl 4'(12-dodecyloxy)biphenyl-4-carboxylate (0.007 mol) was dissolved in ethanol (50 mL) then
reaction mixture refluxed until yellow color precipitate thrown out. After completion of reaction,
the desired product was filtered out and washed with ethanol, then the product recrystallized
from ethanol to get yellowish brown powder (Yield: 70%).
21: C56H71N3O5: FT-IR (KBr pellet, cm-1); 3393, 3066, 2919, 2851, 2344, 1729, 1602,
1584, 1474, 1414, 1291, 1250, 1199, 1142, 1079, 832; 1H NMR (CDCl3, 400 MHz) δ (ppm):
8.51 (s, H, -CH=N-), 8. 12 (m, 2H, Ar-H), 7.94-7.88 (m, 3H, Ar-H), 7.79-7.64 (m, 5H, Ar-H), 7.
46- 7.43 (m, 2H, Ar-H), 7.19 (m, 2H, Ar-H), 7.06-6.85 (m, 4H, Ar-H), 4.06- 3.94 (m, 4H, OCH2-), 3.64 (t, 1H, -OH), 3.51 (m, 2H, -CH2-OH), 1.83 -1.77 (m, 4H, -CH2-), 1.53 -1.43 (m,
4H, -CH2-), 1.31-1.27 (m, 32H, -CH2-), 0. 98 (m, 3H, -CH3).
13
C NMR (CDCl3, 400 MHz) δ
6
(ppm): 165.4, 161.7, 160.8, 151.4, 150.2, 147.2, 146.1, 137. 1, 132.4, 131.5, 129.6, 129.1, 127.4,
124.2, 123.1, 121.5, 120.1, 116.1, 114.2, 68.3, 62.1, 31.6, 30.3, 29.6, 27.1, 25.7, 22.1 and 14.3.
Synthesis of monomers
Synthesis
of
3-(4-(4-(dodecyloxy)benzoyloxy)benzoyloxy)phenyl
4-((E)-(4-((E)-(4-(12-
(methacryloyloxy)dodecyloxy)phenyl)diazenyl)phenylimino)methyl)benzoate
(AZBM-1)
(11)
The typical procedure for the synthesis of monomer (AZBM-1) is as follows: 3-(4-(4(dodecyloxy)benzoyloxy)benzoyloxy)phenyl4-((E)-(4-((E)-(4-(12-hydroxydodecyloxy) phenyl)
diazenyl)phenylimino)methyl)benzoate (0.004 mol) and triethylamine ( 0.004 mol) were
dissolved in dry THF under nitrogen atmosphere and reaction cooled around 5-10 ºC with
constant stirring. Then methacryloyl chloride (0.004 mol) was added dropwise to the reaction
mixture over a period of 30 min and reaction mixture warmed to room temperature with constant
stirring for another 12 h. After completion of reaction precipitated amine hydrochloride was
filtered out and solvent removed from filtrate under vacuum. The crude product was extracted
using ethyl acetate, washed with aqueous hydrochloric acid, brine solution and dried over
anhydrous sodium sulfate. The solvent was removed under vacuum; then, the resulting residue
was purified by column chromatography (silica-gel, hexane and ethyl acetate (9:1) to give yellow
colored solid of monomer (AZBM-1) (Yield: 70%).
11 (AZBM-1): C68H79N3O10: FT-IR (KBr pellet, cm-1); 3060, 2922, 2852, 2344, 1732,
1706, 1602, 1401, 1508, 1252, 1203, 1130, 1059, 828; 1H NMR (400 MHz, CDCl3) δ ppm: 8.30
(m, 1H,-CH=N-), 8.27-8.17 (m, 4H,-Ar-H), 7.90-7.70 (m, 4H,-Ar-H), 7.65-7.60 (m, 4H,-Ar-H),
7.53-7.38 (m, 4H,-Ar-H), 7.01 -6.98 (m, 4H,-Ar-H), 5.86 (s, 1H, -CH2=C(CH3)-), 5.51 (s, 1H,
CH2=C(CH3)-), 4.18-4.08 (m, 4H,-CH2-O-), 3.51 (m, 2H, -CH2-OOC),
2.09 (t, 3H,
7
(CH3)C=CH2-), 1.85 -1.83 (m, 4H-CH2), 1.52-1.12 (m, 28H, -CH2-), 0.88 (t, 3H-CH3).13C NMR
(CDCl3, 400 MHz) δ (ppm): 166.9(CH2=C(CH3)COO-), 165.2 (Ar-COO), 162.3 (Ar-O-CH2-),
160.2 (imine), 156.4, 154.4 (Ar-O-CH2-), 151.2, 149.0, 146.7, 144.6 (azo), 142.4, 137.2, 136.5,
135.2 (CH2=C(CH3)COO-), 131.8, 127.1, 125.0 (CH2=C(CH3)COO), 122.1, 119.4, 114.9
(aromatic), 68.5 (Ar-O-CH2-), 62.7 (CH2=C(CH3)COO-CH2-), 34.2, 30.5, 27.1, 24.4, 20.18
(CH2=C(CH3)COO-), and 14.5 (aliphatic).
Synthesis
of
4-((3-((E)-(4-((E)-(4-(12-(methacryloyloxy)
dodecyloxy)
phenyl)
diazenyl)phenylimino)methyl)phenoxy)carbonyl)phenyl 4-(dodecyloxy)benzoate (AZBM-2)
(15)
The monomer AZBM-2 was synthesized and synthetic procedure was followed earlier
preparation
(AZBM-1)
using
4-((3-((4-((4-(12-hydroxydodecyloxy)
phenylimino)methyl)phenoxy)carbonyl)phenyl
phenyl)
4-(12-dodecyloxy)benzoate
diazenyl)
(0.004
mol),
triethylamine ( 0.004 mol) and methacryloyl chloride (0.004 mol).
15 (AZBM-2): C61H71N3O8: FT-IR (KBr pellet, cm-1); 2921, 2851, 2344, 1735, 1717,
1603, 1560, 1406, 1262, 1163, 1105, 1084, 845; 1H NMR (400 MHz, CDCl3) δ ppm: 8.37 (m,
1H,-CH=N-), 7. 89-7.87 (m, 6H,-Ar-H), 7.72 (m, 4H,-Ar-H), 7.61 (m, 2H,-Ar-H),7.26 (m, 2H,Ar-H), 7.06-6.98 (m, 4H,-Ar-H), 6.88 (m, 2H,-Ar-H), 6.09 (s, 1H, -CH2=C(CH3)-), 5.51 (s, 1H,
CH2=C(CH3)-), 4.15-4.02 (m, 4H,-CH2-OH), 3.88 (m, 2H, -CH2-OOC), 2.09 (t, 3H, (CH3)C=
CH2-), 1.85 -1.83 (m, 4H,-CH2-), 1.52-1.25 (m, 28H, -CH2-), 0.89 (t, 3H-CH3).13C NMR (CDCl3,
400 MHz) δ (ppm): 166.5(CH2=C(CH3)COO-), 164.5 (Ar-COO) , 162.0 (Ar-O-), 158.4 (imine),
155.1(Ar-O-), 152.8, 150.3, 149.0, 146.8 (azo), 142.0, 140.3, 137.5 (CH2=C(CH3)COO-), 132.6,
129.0, 126.9, 124.1(CH2=C(CH3)COO-), 122.9, 118.3, 116.9, 114.4 (aromatic), 68.4 (Ar-O-
8
CH2-), 64.4 (CH2=C(CH3)COO-CH2-), 30.2, 28.2, 27.3, 23.6, 20.6 (CH2=C(CH3)COO-) and
14.5.
Synthesis
of
3-((E)-(4-((E)-(4-(12-(methacryloyloxy)dodecyloxy)
phenyl)
diazenyl)
phenylimino)methyl)phenyl4'-(dodecyloxy) biphenyl-4- carboxylate (AZBM-3) (22)
The monomer AZBM-3 was synthesized and synthetic procedure was followed earlier
preparation (AZBM-1) using 3-((4-((4-(12-hydroxy dodecyloxy)phenyl)diazenyl) phenylimino)
methyl) phenyl 4'-(dodecyloxy)biphenyl-4-carboxylate (0.004 mol), triethylamine ( 0.004 mol)
and methacryloyl chloride (0.004 mol).
22 (AZBM-3): C60H75N3O6: FT-IR (KBr pellet, cm-1); 3058, 2921, 2851, 2345, 1717,
1617, 1401, 1293, 1262, 1200, 1164, 1030, 832; 1H NMR (400 MHz, CDCl3) δ ppm: 8.37 (m,
1H,-CH=N-), 8.27-8.22 (m, 4H,-Ar-H), 8.15-8.02 (m, 4H,-Ar-H), 7.89-7.60 (m, 4H,-Ar-H),
7.53-7.35 (m, 4H,-Ar-H), 7.23-7.14 (m, 4H,-Ar-H), 7.00-6.98 (m, 4H,-Ar-H), 6.23 (s, 1H, CH2=C(CH3)-), 5.71 (s, 1H, CH2=C(CH3)-), 4.15-4.03 (m, 4H,-CH2-OH), 3.64 (m, 2H, -CH2OH), 2.19 (t, 3H, (CH3)C= CH2-), 1.94-1.78 (m, 4H-CH2-), 1.52-1. 25 (m, 28H, -CH2-), 0.87 (t,
3H-CH3).13C NMR (CDCl3, 400 MHz) δ (ppm): 166.3(CH2=C(CH3)COO-), 164.2 (Ar-COO-),
162.8 (Ar-O-CH2-), 160.3 (imine), 155.6 (Ar-O-CH2-), 152.4, 150.9, 148.2, 144.8 (azo), 140.7,
137.4 (CH2=C(CH3)COO-), 130.7, 132.4, 131.9, 130.7, 129.7, 124.8 (CH2=C(CH3)COO-),
123.7, 122.3, 119.5, 115.8, 114.5 (aromatic), 68.3 (Ar-O-CH2-), 64.6 (CH2=C(CH3)COO-CH2-),
32.0, 29.3, 25.9, 22.8, 18.7 (CH2=C(CH3)COO-), and 14.1 (aliphatic).
Synthesis of Polymers
Synthesis of Polymer (AZBP-1) (12)
The polymer (AZBP-1) was synthesized by a free radical polymerization technique from
the corresponding monomer (AZBM-1) using AIBN as an initiator in THF at 60 ºC. The
9
AZBM-1 (0.003 mol) and AIBN (2wt %) were dissolved in dry THF and a gentle steam of
nitrogen purged into the solution. The solution was kept in an oil bath at 60 ºC for 24 h. Then,
the solution was cooled and poured into excess of methanol to precipitate the product. Crude
polymer thus obtained was re-precipitated twice using chloroform and hexane. Purified polymer
was dried at 45 ºC under vacuum for 12 h to afford yellow colored powder. Similar procedure
was adapted for preparation of other polymer such as AZBP-2 & 3 corresponding monomers
(AZBM-2 & 3)
12 (AZBP-1): C68H79N3O10: FT-IR (KBr pellet, cm-1); 3025, 2934, 2861, 2345, 1735,
1602, 1508, 1405, 1255, 1206, 1161, 1060, 845; 1H NMR (400 MHz, CDCl3) δ ppm: 8.44 (m,
1H,-CH=N-), 7.90-7.88 (m, 4H,-Ar-H), 7.73-7.07 (m, 4H,-Ar-H), 7. 64 (m, 4H,-Ar-H), 7.33-7.31
(m, 4H,-Ar-H), 7.20 -7.17 -6.98 (m, 4H,-Ar-H), 4.06-4.14 (m, 4H,-CH2-OH), 3.73 (m, 2H, -CH2O-), 1.84-1.79 (m, 6H-CH2), 1.53-1.12 (m, 38H, -CH2-), 0.88 (t, 3H-CH3).
13
C NMR (CDCl3,
400 MHz) δ (ppm): 167.1 (Ar-COO), 163.5 (Ar-O-CH2-), 159.7 (imine), 157.5, 152.7 (Ar-OCH2-), 152.7, 150.9, 148.9, 145.8 (azo), 142.7, 138.6, 137.9, 133.1, 127.8, 124.3, 121.0, 119.5
(aromatic), 68.3 (Ar-O-CH2-), 64.7 (-COO-CH2-), 34.2, 33.7, 30.6, 27.2, 25.8, 24.1, 19.3, 17.2
and 14.3 (aliphatic).
15 (AZBP-2): C61H71N3O8: FT-IR (KBr pellet, cm-1); C,74.89; H7.73; N, 4.53; O,
13.08: 2920, 2851, 2345, 1738, 1623, ,1526, 1401, 1254, 1195, 1154, 1107, 843. 1H NMR (400
MHz, CDCl3) δ ppm: 8.23 (m, 1H,-CH=N-), 7.83-7.73 (m, 4H,-Ar-H), 7.72(m, 4H,-Ar-H),
7.63(m, 6H,-Ar-H), 7.54(m, 2H,-Ar-H), 7.02 (m, 4H,-Ar-H), 4.03 (m, 4H,-CH2-O-), 3.50 (m,
2H, -CH2-OOC-), 1.82 (m, 4H-CH2-), 1.58-1.48 (m, 8H, -CH2-), 1.25-1.22 (t, 30H-CH3), 0.88 (t,
6H-CH3).13C NMR (CDCl3, 400 MHz) δ (ppm): 166.5 (Ar-COO), 164.6, 161.5 (Ar-O-CH2-),
159.6 (imine), 158.5, 154.5(Ar-O-CH2-), 151.6, 153.4, 148.8, 145.8, 141.6, 131.6, 130.9, 129.7,
10
128.5, 125.0, 120.7, 119.3, 115.2 (aromatic), 68.6 (Ar-O-CH2-), 64.3(-COO-CH2-), 38.7, 29.7,
29.3, 26.3, 25.1, 24.1, 21.9, 17.51 and 14.1 (aliphatic).
23 (AZBP-3): C60H75N3O6: FT-IR (KBr pellet, cm-1); C,77.14; H, 8.09; N, 4.50; O,
10.28: 3068, 2919, 2851, 2345, 1718, 1603, 1404, 1292, 1200, 1135, 1084, 832. 1H NMR (400
MHz, CDCl3) δ ppm: 8.23 (m, 1H,-CH=N-), 8.15 (m, 4H,-Ar-H), 8.04-7.83 (m, 4H,-Ar-H),
7.78-7.55 (m, 4H,-Ar-H), 7.43-7.33 (m, 4H,-Ar-H), 7.27-7.18 (m, 8H,-Ar-H), 6.98 (m, 4H,-ArH), 4.03 (m, 4H,-CH2-O-Ar), 3.64 (m, 2H, -CH2-OOC-), 1.82 (m, 4H-CH2), 1.52-1.48 (m, 6H, CH2-), 1. 25 (m, 22H, -CH2-), 0.88 (t, 6H-CH3).13C NMR (CDCl3, 400 MHz) δ (ppm): 166.4
(Ar-COO), 160.8 (Ar-O-CH2-), 158.8 (imine), 155.9 (Ar-O-CH2-), 152.3, 150.6, 146.9, 145.8
(azo), 140.9, 139.8, 136.2, 134.1, 131.9, 130.7, 129.0, 127.8, 125.6, 124.0, 122.2, 118.9, 114.5
(aromatic), 68.0 (Ar-O-CH2-), 65.1(-COO-CH2-), 31.6, 29.6, 24.9, 20.8, 17.8 and 14.1
(aliphatic).
Synthesis of the following compounds (4-(4'-hydroxyphenylazo)phenyl)acetamide (1)1,
resorcinol monobenzyl ether (4), 4-(4'-(n-alkyloxy) benzoyloxy)benzaldehyde (5), 4-(4'-(nalkyloxy)benzoyloxy)benzoic
acid
(6),
4-((3-(benzyloxy)phenoxy)
carbonyl)phenyl-4-
(hexyloxy)benzoate (7), 4-((3-hydroxyphenoxy) carbonyl) phenyl-4-(hexyloxy) benzoate (8) and
3-(4-(4-(hexyloxy)benzoyloxy) benzoyloxy)phenyl 4-formylbenzoate (9) were carried out
according to our previous report 2. The synthesis of the following compounds ethyl 4'hydroxybiphenyl-4-carboxylate
dodecyloxybiphenyl-4-carboxylic
(17),
acid
4'-6-hexyloxybiphenyl-4-carboxylate
(19),
Synthesis
of
(18),
4'-12-
3-formylphenyl
4'-12-
dodecyloxybiphenyl-4-carboxylate (20) were carried out according to previous report 3.
11
Figure S1
Figure S2
Representative FT-IR spectral data of monomer AZBM-1
Representative FT-IR spectral data of polymer AZBP-1
12
Figure S3
Figure S4
Representative 1H NMR spectral data of monomer AZBM-3
Representative 1H NMR spectral data of polymer AZBP-3
13
References
1
Vijaysrinivasan, M.; Kannan, P.; Roy, A. Liq Cryst. doi.org/10.1080/02678292.2012.721904
2
Balamurugan, S.; Kannan, P.; Yadupati, K.; Roy. A. J Mol Struct 2011, 1001,118-124.
3
Veena, P. Liq Cryst 2001, 28, 1115- 1120.