Supporting Information
Effects of polyethylene spacer length in polymeric electrolytes on gelation of ionic
liquids and ionogel properties
Jun'ichi Nagasawa,1 Sonoko Wakahara,1 Hajime Matsumoto,2 Hideyuki Kihara,1 Masaru Yoshida1,*
1
Nanosystem Research Institute, National Institute of Advanced Industrial Science and Technology
(AIST), Tsukuba, Ibaraki 305-8565, Japan
2
Research Institute for Ubiquitous Energy Devices, National Institute of Advanced Industrial Science
and Technology (AIST), Ikeda, Osaka 563-8577, Japan
Synthesis and characterization of polymers
Poly[(dimethyliminio)ethane-1,2-diyl(dimethyliminio)methylene-1,4-phenylenecarbonylimino-trans-cy
clohexane-1,4-diyliminocarbonyl-1,4-phenylenemethylene dichloride] (CDBA2•Cl)
To a stirred suspension of 4,4′-bis(chloromethyl)-N,N′-(trans-cyclohexane-1,4-diyl)di(benzamide)1 (1)
(838 mg, 2.0 mmol) in N,N-dimethylformamide (70 mL) at 80°C was added N,N,N',N'-tetramethylethylenediamine (232 mg, 2.0 mmol) in N,N-dimethylformamide (10 mL). The mixture was stirred at
80°C for 48 h to give CDBA2•Cl as precipitates. The precipitates were filtered off using a 0.2-µm filter,
washed with N,N-dimethylformamide and acetone, and dried in a vacuum desiccator over phosphorus
pentoxide; yield 8.51 g (78%). 1H NMR (400 MHz, D2O, δ): 1.50-1.70 (m, 4H, cyclohexane ring CHH),
2.04-2.20 (m, 4H, cyclohexane ring CHH), 2.95), 3.24 (s, 12H, CH3), 3.85-4.00 (m, 2H, CH), 4.03-4.24 (m,
4H, NCH2CH2N), 4.75 (br s, 4H, ArCH2), 7.64-7.80 (m, 4H, aromatic CH), 7.85-7.97 (m, 4H, aromatic
CH) ppm. Anal. calcd for (C28H40Cl2N4O2•(H2O)0.5)n: C 61.76, H 7.59, N 10.31; found: C 61.49, H 7.79, N
10.35.
Poly[(dimethyliminio)ethane-1,2-diyl(dimethyliminio)methylene-1,4-phenylenecarbonylimino-trans-cy
clohexane-1,4-diyliminocarbonyl-1,4-phenylenemethylene
bis(trifluoromethanesulfonyl)amide]
(CDBA2•TFSA)
To a solution of CDBA2•Cl (429 mg) in water (50 mL) at 100°C was added a solution of lithium
bis(trifluoromethanesulfonyl)amide (2.30 g, 8.0 mmol) in water (14 mL). The mixture was stirred for 10
min and left to cool to room temperature. The precipitates were filtered off using a 0.2-µm filter and
washed with water. The precipitates was dried in the air, then in a vacuum desiccator over phosphorus
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pentoxide; yield 721 mg (89%). 1H NMR (400 MHz, DMSO-d6, δ): 1.40-1.60 (m, 4H, cyclohexane ring
CHH), 1.82-2.00 (m, 4H, cyclohexane ring CHH), 3.07 (s, 12H, CH3), 3.75-3.89 (m, 2H, CH), 3.92-4.00
(m, 4H, NCH2CH2N), 4.67 (br s, 4H, ArCH2), 7.71 (br d, J = 7.4 Hz, 4H, aromatic CH), 8.03 (br d, J = 7.4
Hz, 4H, aromatic CH), 8.42 (br d, J = 7.4 Hz, 2H, NH) ppm. Anal. calcd for (C32H40F12N6O10S4)n: C 37.50,
H 3.93, N 8.20; found: C 37.78, H 3.80, N 8.38.
Poly[(dimethyliminio)ethane-1,2-diyl(dimethyliminio)methylene-1,4-phenylenecarbonylimino-trans-cy
clohexane-1,4-diyliminocarbonyl-1,4-phenylenemethylene bis(fluorosulfonyl)amide] (CDBA2•FSA)
CDBA2•FSA was synthetized from CDBA2•Cl (802 mg) and potassium bis(fluorosulfonyl)amide
(1.61 g, 7.3 mmol). Yield 1.05 g (86%). 1H NMR (400 MHz, DMSO-d6, δ): 1.40-1.60 (m, 4H, cyclohexane
ring CHH), 1.83-2.01 (m, 4H, cyclohexane ring CHH), 3.08 (s, 12H, CH3), 3.75-3.91 (m, 2H, CH),
3.92-4.12 (m, 4H, NCH2CH2N), 4.68 (br s, 4H, ArCH2), 7.72 (br d, J = 7.6 Hz, 4H, aromatic CH), 8.03 (br
d, J = 7.6 Hz, 4H, aromatic CH), 8.43 (br d, J = 7.4 Hz, 2H, NH) ppm. Anal. calcd for
(C28H40F4N6O10S4•(H2O)0.5)n: C 40.33, H 4.96, N 10.08; found: C 40.19, H 5.01, N 9.91.
Poly[(dimethyliminio)butane-1,4-diyl(dimethyliminio)methylene-1,4-phenylenecarbonylimino-trans-cy
clohexane-1,4-diyliminocarbonyl-1,4-phenylenemethylene dichloride] (CDBA4•Cl)
CDBA4•Cl
was
synthetized
from
compound
1
(419
mg,
1.0
mmol)
and
N,N,N′,N′-tetramethyl-1,4-diaminobutane (144 mg, 1.0 mmol). Yield 448 mg (77%). 1H NMR (400 MHz,
D2O, δ): 1.50-1.68 (m, 4H, cyclohexane ring CHH), 1.87-2.19 (m, 8H, NCH2CH2, cyclohexane ring CHH),
3.10 (s, 12H, CH3), 3.34-3.55 (m, 4H, NCH2CH2), 3.83-4.00 (m, 2H, CH), 4.61 (br s, 4H, ArCH2), 7.69 (br
d, J = 7.8 Hz, 4H, aromatic CH), 7.89 (br d, J = 7.8 Hz, 4H, aromatic CH) ppm. Anal. calcd for
(C30H44Cl2N4O2•H2O)n: C 61.95, H 7.97, N 9.63; found: C 61.85, H 7.82, N 9.60.
Poly[(dimethyliminio)butane-1,4-diyl(dimethyliminio)methylene-1,4-phenylenecarbonylimino-trans-cy
clohexane-1,4-diyliminocarbonyl-1,4-phenylenemethylene
bis(trifluoromethanesulfonyl)amide]
(CDBA4•TFSA)
CDBA4•TFSA
was
synthetized
from
CDBA4•Cl
(282
mg)
and
lithium
bis(trifluoromethanesulfonyl)amide (718 g, 2.5 mmol). Yield 496 mg (97%). 1H NMR (400 MHz,
DMSO-d6, δ): 1.40-1.60 (m, 4H, cyclohexane ring CHH), 1.73-2.04 (m, 8H, NCH2CH2, cyclohexane ring
CHH), 2.99 (s, 12H, CH3), 3.22-3.42 (m, 4H, NCH2CH2), 3.73-3.92 (m, 2H, CH), 4.59 (br s, 4H, ArCH2),
7.66 (br d, J = 7.9 Hz, 4H, aromatic CH), 8.01 (br d, J = 7.9 Hz, 4H, aromatic CH), 8.41 (br d, J = 7.1 Hz,
S2
2H, NH) ppm. Anal. calcd for (C34H44F12N6O10S4)n: C 38.78, H 4.21, N 7.98; found: C 38.94, H 4.06, N
8.16.
Poly[(dimethyliminio)butane-1,4-diyl(dimethyliminio)methylene-1,4-phenylenecarbonylimino-trans-cy
clohexane-1,4-diyliminocarbonyl-1,4-phenylenemethylene bis(fluorosulfonyl)amide] (CDBA4•FSA)
CDBA4•FSA was synthetized from CDBA4•Cl (1.01 g) and potassium bis(fluorosulfonyl)amide (1.97
g, 9.0 mmol). Yield 1.42 g (96%). 1H NMR (400 MHz, DMSO-d6, δ): 1.39-1.59 (m, 4H, cyclohexane ring
CHH), 1.73-2.03 (m, 8H, NCH2CH2, cyclohexane ring CHH), 2.98 (s, 12H, CH3), 3.22-3.45 (m, 4H,
NCH2CH2), 3.74-3.91 (m, 2H, CH), 4.58 (br s, 4H, ArCH2), 7.66 (br d, J = 7.8 Hz, 4H, aromatic CH), 8.00
(br d, J = 7.8 Hz, 4H, aromatic CH), 8.40 (br d, J = 6.8 Hz, 2H, NH) ppm. Anal. calcd for
(C30H44F4N6O10S4)n: C 42.24, H 5.20, N 9.85; found: C 42.36, H 5.15, N 9.64.
Poly[(dimethyliminio)decane-1,10-diyl(dimethyliminio)methylene-1,4-phenylenecarbonylimino-trans-cyclohexane-1,4-diylim
inocarbonyl-1,4-phenylenemethylene dichloride] (CDBA10•Cl)
CDBA10•Cl
was
synthetized
from
compound
1
(1.68
g,
4.0
mmol)
and
1,10-bis(dimethylamino)decane2 (914 mg, 4.0 mmol). Yield 2.44 g (92%). 1H NMR (400 MHz, D2O, δ):
1.24-1.63 (m, 16H, NCH2CH2CH2CH2CH2, cyclohexane ring CHH), 1.78-2.15 (m, 8H, NCH2CH2,
cyclohexane ring CHH), 3.07 (s, 12H, CH3), 3.17-3.35 (m, 4H, NCH2CH2), 3.67-3.92 (m, 2H, CH), 4.55
(br s, 4H, ArCH2), 7.67 (br d, J = 8.0 Hz, 4H, aromatic CH), 7.88 (br d, J = 8.0 Hz, 4H, aromatic CH)
ppm. Anal. calcd for (C36H56Cl2N4O2•H2O)n: C 64.94, H 8.78, N 8.42; found: C 65.12, H 8.75, N 8.57.
Poly[(dimethyliminio)decane-1,10-diyl(dimethyliminio)methylene-1,4-phenylenecarbonylimino-trans-c
yclohexane-1,4-diyliminocarbonyl-1,4-phenylenemethylene
bis(trifluoromethanesulfonyl)amide]
(CDBA10•TFSA)
CDBA10•TFSA
was
synthetized
from
CDBA10•Cl
(973
mg)
and
lithium
bis(trifluoromethanesulfonyl)amide (4.31 g, 15 mmol). Yield 1.55 mg (93%). 1H NMR (400 MHz,
DMSO-d6, δ): 1.20-1.56 (m, 16H, NCH2CH2CH2CH2CH2, cyclohexane ring CHH), 1.71-1.98 (m, 8H,
NCH2CH2, cyclohexane ring CHH), 2.94 (s, 12H, CH3), 3.20-3.35 (m, 4H, NCH2CH2), 3.73-3.87 (m, 2H,
CH), 4.54 (br s, 4H, ArCH2), 7.63 (br d, J = 7.3 Hz, 4H, aromatic CH), 7.98 (br d, J = 7.3 Hz, 4H,
aromatic CH), 8.40 (br d, J = 7.4 Hz, 2H, NH) ppm. Anal. calcd for (C40H56F12N6O10S4)n: C 42.25, H 4.96,
N 7.39; found: C 42.13, H 4.78, N 7.37.
S3
Poly[(dimethyliminio)decane-1,10-diyl(dimethyliminio)methylene-1,4-phenylenecarbonylimino-trans-c
yclohexane-1,4-diyliminocarbonyl-1,4-phenylenemethylene bis(fluorosulfonyl)amide] (CDBA10•FSA)
CDBA10•FSA was synthetized from CDBA10•Cl (701 mg) and potassium bis(fluorosulfonyl)amide
(1.33 g, 6.1 mmol). Yield 863 mg (87%). 1H NMR (400 MHz, DMSO-d6, δ): 1.22-1.55 (m, 16H,
NCH2CH2CH2CH2CH2, cyclohexane ring CHH), 1.72-1.98 (m, 8H, NCH2CH2, cyclohexane ring CHH),
2.94 (s, 12H, CH3), 3.20-3.34 (m, 4H, NCH2CH2), 3.74-3.86 (m, 2H, CH), 4.54 (br s, 4H, ArCH2), 7.63 (br
d, J = .7.8 Hz, 4H, aromatic CH), 7.98 (br d, J = 7.8 Hz, 4H, aromatic CH), 8.39 (br d, J = 7.5 Hz, 2H,
NH) ppm. Anal. calcd for (C36H56F4N6O10S4•(H2O)0.5)n: C 45.70, H 6.07, N 8.88; found: C 45.61, H 5.99,
N 8.88.
(a)
8
20
50
100 g/L
6
10
50
(b)
3
100 g/L
Figure S1. Photographs of ionogels at varying concentration concentrations. (a)
CDBA2•TFSA/[EMI][TFSA] (b) CDBA10•FSA/[EMI][FSA].
S4
(a)
(b)
160
160
[BMI][TFSA]
CDBA4•TFSA
CDBA6•TFSA
140
120
120
100
100
Tgel [°C]
Tgel [°C]
140
80
60
[P13][TFSA]
80
60
40
40
20
20
0
CDBA4•TFSA
CDBA6•TFSA
CDBA10•TFSA
0
0
20
40
60
80
100
0
20
Concentration [g/L]
60
80
100
Concentration [g/L]
(c)
(d)
160
160
[BMI][FSA]
140
CDBA4•FSA
CDBA6•FSA
CDBA10•FSA
120
[P13][FSA]
140
120
100
Tgel [°C]
Tgel [°C]
40
80
60
100
80
60
40
40
20
20
0
CDBA4•FSA
CDBA6•FSA
CDBA10•FSA
0
0
20
40
60
80
100
0
Concentration [g/L]
20
40
60
80
100
Concentration [g/L]
Figure S2. Thermal transitions of ionogels upon heating. Close and open marks indicate the start and
end points of gel-sol transitions, respectively. (a) Ionogels of CDBAm•TFSA in [BMI][TFSA]. (b)
Ionogels of CDBAm•FSA in [P13][TFSA]. (c) Ionogels of CDBAm•TFSA in [BMI][FSA]. (d)
Ionogels of CDBAm•FSA in [P13][TFSA]. Ionogels of CDBA2•TFSA and CDBA2•FSA did not
begin transitioning to the sol state in any of these ILs before reaching 155°C. The CDBA6•TFSA and
CDBA6•FSA data were reported previously.1
S5
(a)
(b)
6
6
10
5
10
4
10
10
5
10
4
G', G" [Pa]
G', G" [Pa]
10
3
10
2
3
10
2
10
10
G' (50 g/L)
G' (30 g/L)
G' (10 g/L)
1
10
G" (50 g/L)
G" (30 g/L)
G" (10 g/L)
G" (50 g/L)
G" (30 g/L)
G" (10 g/L)
0
0
10
0.01
G' (50 g/L)
G' (30 g/L)
G' (10 g/L)
1
10
0.1
1
10
0.01
10
0.1
1
10
100
Strain [%]
Frequency [Hz]
Figure S3. Rheological data of CDBA2•FSA/[EMI][FSA] ionogels. (a) Frequency sweeps of three
ionogel samples at varying concentrations. (b) Strain amplitude sweeps.
(a)
(b)
5
6
10
5
10
10
4
10
4
3
G', G" [Pa]
G', G" [Pa]
10
3
10
2
10
10
2
10
1
10
1
10
G' (70 g/L)
G' (50 g/L)
G' (30 g/L)
0
10
G" (70 g/L)
G"(50 g/L)
G"(30 g/L)
0
10
G" (70 g/L)
G" (50 g/L)
G" (30 g/L)
-1
10
-1
10
0.01
G' (70 g/L)
G' (50 g/L)
G' (30 g/L)
0.1
1
0.01
10
0.1
1
10
100
Strain [%]
Frequency [Hz]
Figure S4. Rheological data of CDBA4•TFSA/[EMI][TFSA] ionogels. (a) Frequency sweeps of three
ionogel samples at varying concentrations. (b) Strain amplitude sweeps.
S6
(a)
(b)
6
6
10
10
5
5
10
4
10
10
4
G',G" [Pa]
G', G" [Pa]
10
3
10
2
10
3
10
2
10
1
10
1
10
G' (50 g/L)
G' (30 g/L)
G' (10 g/L)
G' (5 g/L)
0
10
G’ (50g/L)
G’ (30g/L)
G’ (10g/L)
G’ (5g/L)
0
G" (50 g/L)
G" (30 g/L)
G" (10 g/L)
G“ G" (5 g/L)
10
-1
10
-1
G“ (50g/L)
G“ (30g/L)
G“ (10g/L)
G“ (5g/L)
-2
10
10
0.01
0.1
1
10
0.01
0.1
Frequency [Hz]
1
10
100
Strain [%]
Figure S5. Rheological data of CDBA10•FSA/[EMI][FSA] ionogels. (a) Frequency sweeps of three
ionogel samples at varying concentrations. (b) Strain amplitude sweeps.
(a)
(b)
5
5
Strain Gc
CDBA2·TFSA/[EMI][TFSA]
CDBA4·TFSA/[EMI][TFSA]
CDBA6·TFSA/[EMI][TFSA]
Strain Gc
CDBA2·FSA/[EMI][FSA]
CDBA4·FSA/[EMI][FSA]
4
10
4
10
3
10
2
10
4
Strain Gc
CDBA6·FSA/[EMI][FSA]
CDBA10·FSA/[EMI][FSA]
3
10
3
10
2
10
2
2
10
1
10
1
10
10
1
0
10
10
0
20
40
60
1
0
10
80
10
0
20
40
60
10
80
Concentration [g/L]
Concentration [g/L]
Figure S6. Rheological data of CDBAm•TFSA/[EMI][TFSA] and CDBAm•FSA/[EMI][FSA]
ionogels. Strains and moduli at the values where G′ and G″ crossed were plotted against concentration
of (a) CDBAm•TFSA and (b) CDBAm•FSA. The CDBA6•TFSA and CDBA6•FSA data were
reported previously.1
S7
Gc [Pa]
3
10
Gc [Pa]
Strain [%]
10
10
Strain [%]
4
10
5
5
10
10
Figure S7. Photograph of a 50-g/L CDBA6·FSA/[EMI][FSA] ionogel. The gel size is 8 × 8 × 20 mm.
References
1. J. Nagasawa, H. Matsumoto, M. Yoshida. ACS Macro Lett. 2012, 1, 1108-1112.
2. S. Souirti, M. Baboulene. Can. J. Chem. 2003, 81, 883-888.
S8