Supplementary Information
Synthesis
and
properties
of
conjugated
polymers
from
3,6-di(4-chlorophenyl)-
3,6-dihydrophthalic acid diethyl ester and application to the photo-sensitizer of a solar cell
Atsushi Morikawa* and Hirotoshi Kakuta
Department of Biomolecular Functional Engineering, Ibaraki University,
Hitachi, Ibaraki, 316-8511, Japan
1. Synthesis of 5
4-Chlorocinnamaldehyde
In a three-necked flask, 4-chlorobenzaldehyde (42.4 g, 0.4 mol) was added to a solution of
sodium hydroxide (4.00 g, 0.1 mol) in water (200 mL) in one portion at 0°C. Methanol (20mL)
was added to the mixture to dissolve the 4-chlorobenzaldehyde phase.
After 90% acetaldehyde
(19.6 g, 0.4 mol) was added to the mixture at 0°C, the reaction mixture was stirred at room
temperature for 12 h under nitrogen.
The reaction mixture was extracted three times with
dichloromethane (150 mL), and the combined organic layer was dried over anhydrous magnesium
sulfate.
After the solvent was evaporated, pure 4-chlorocinnamaldehyde was obtained by
fractional distillation.
Yield: 14.0 g (21 %).
Bp: 86-92°C (1 torr).
The IR spectrum exhibited
absorption bands at 1680 cm-1 (C=O) and 1625 cm-1 (C=C).
1
H1
H2
H3
Cl
O
H4
H5
The 1H NMR spectrum [δ in CDCl3] showed signals at 6.70 (dd, 1H, J = 12.6 Hz, J = 7.3 Hz,
H4), 6.72 (d, 1H, J = 12.6 Hz, H3), 7.41 (d, 2H, J = 8.8 Hz, H1), 7.51 (d, 2H, J = 8.8 Hz, H2) and
9.75 (d, 1H, J = 7.3 Hz, H5). The 13C NMR spectrum [δ in CDCl3] showed signals at 127.01,
129.46, 129.98, 132.51, 134.22, 135.78 and 186.53 ppm.
Anal. Calcd for C9H7ClO: C, 64.88%; H, 4.24%. Found: C, 64.61%; H, 4.18%.
(E,E)-1,4-Di (4-chlorophenyl)-1,3-butadiene (5)
A solution of 4-chlorobenzylchloride (17.7 g, 0.11 mol) and triphenylphosphine (26.2 g, 0.10
mol) in toluene (150 mL) was heated at reflux temperature for 12 h.
After the reaction mixture
was cooled to room temperature, the precipitated product was collected by filtration, washed
thoroughly with toluene, and the obtained phosphonium chloride was dried under vacuum.
In a three-necked flask, the phosphonium chloride (21.2 g, 0.05 mol) was added to a sodium
ethoxide solution prepared from sodium (1.15 g, 0.05 mol) and anhydrous ethanol (200 mL), and
the mixture was stirred at room temperature for 10 min under nitrogen.
A solution of
4-chlorocinnamaldehyde (8.33 g, 0.05mol) in anhydrous ethanol (40 mL) was added to the mixture.
After the reaction mixture was stirred at room temperature for 2 h, the solvent was evaporated.
The residue was washed thoroughly with water, and dried.
recrystallization from acetic acid.
Yield: 6.19 g (45%).
Pure 5 was obtained by
Mp: 156-158°C.
The IR spectrum
exhibited absorption bands at 1615 cm-1, 1600 cm-1 (C=C) and 1490 cm-1 (aromatic).
2
H1
Cl
H2
H3
H4
Cl
The 1H NMR spectrum [δ in CDCl3] showed signals at 6.72 (d, 2H, J = 12.6 Hz, H3), 6.91 (d,
1H, J = 12.6 Hz, H4), 7.28 (d, 4H, J = 8.8 Hz, H1), and 7.36 (d, 2H, J = 8.8 Hz, H2).
The 13C
NMR spectrum [δ in CDCl3] showed signals at 127.56, 128.86, 129.48, 131.95, 133.27 and 135.72
ppm.
Anal. Calcd for C11H12C2l: C, 69.84%; H, 4.40%.
Found: C, 69.62%; H, 4.29%.
3
2. Ni(0)-Catalyzed Polymerization of 1 and 2.
Entry
Ni(II)
PPh3
compound
1-1 a)
1-2 a)
1-3 a)
1-4 a)
1-5 a)
2-1 b)
2-2 b)
2,2’-
Et4NI
Zn
solvent
bipyridine
NiCl2(PPh3)2
1.5
0.25 mmol
mmol
NiCl2(PPh3)2
1.5
0.25 mmol
mmol
NiBr2
1.9
0.25 mmol
mmol
NiBr2
1.9
0.25 mmol
mmol
NiCl2
1.9
0.25 mmol
mmol
NiCl2(PPh3)2
1.5
0.25 mmol
mmol
NiBr2
1.9
0.25 mmol
mmol
-
-
-
Temp
Yield
DP
(°C)
(%)
(= n+2)
80
75
7.0
80
60
4.8
3.75
15.4
DMF
mmol
mmol
20 mL
3.75
15.4
dioxane
mmol
mmol
20 mL
-
7.72
DMF
80
88
7.4
DMF
100
78
7.0
DMAc
80
58
4.5
80
81
7.0
80
92
6.8
mmol
-
-
7.72
mmol
0.2 mmol
-
7.72
mmol
-
-
3.75
15.4
DMF
mmol
mmol
20 mL
-
7.72
DMF
a)
1 (0.94g, 2.1 mmol) was used in the polymerization.
b)
2 (0.94g, 2.1 mmol) was used in the polymerization.
mmol
4
3. DSC and TG curves of conjugated polymer. (a) DSC, (b) TG in nitrogen, and (c) TG in air.
80
b
60
40
a
210 °C
c
Endo　←　ΔT　→　Exo
Weight Residue (%)
100
20
0
Temperature (°C )
5