Paper
Journal of Materials Chemistry C
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products were then dried at room temperature for several days
under dynamic vacuum.
C-C12Br. Yield: 83.0%. H NMR (298 K, 250 MHz, DMSO-d6)
d ¼ 9.37 (t, 2H), 7.81 (d, 4H), 7.46 (s, 4H), 5.43 (s, 4H), 4.15 (t,
4H), 1.22 (t, 40H), 0.84 (t, 6H).
A-C4Br. Yield: 91%. 1H NMR (298 K, 250 MHz, DMSO-d6)
d ¼ 9.30 (m, 2H), 7.91 (m, 4H), 4.14 (m, 8H), 1.80 (s, 8H), 1.31
(m, 8H), 0.84 (t, 6H).
Elemental analysis (%) calcd for C-C12Br: C 61.95, H 8.76, N
7.60; found: C 62.4, H 9.01, N 7.43.
D-C4Br. Yield: 70%. 1H NMR (298 K, 250 MHz, DMSO-d6)
d ¼ 9.35 (s, 2H), 7.86 (d, 4H), 5.32 (m, 4H), 4.21 (t, 4H), 1.70–1.87
(m, 4H), 1.25 (dt, 4H), 0.90 (t, 6H).
Elemental analysis (%) calcd for A-C4Br: C 48.79, H 7.37, N
11.38; found: C 48.80, H 7.52, N 11.55.
A-C8Br. Yield: 81%. 1H NMR (298 K, 250 MHz, DMSO-d6)
d ¼ 9.45 (m, 2H), 7.95 (m, 4H), 4.22 (m, 8H), 2.08 (s, 8H), 1.25
(m, 24H), 0.79 (t, 6H).
Elemental analysis (%) calcd for D-C4Br: C 46.97, H 6.13, N
12.17; found: C 48.88, H 5.99, N 12.20.
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Elemental analysis (%) calcd for A-C8Br: C 55.63, H 8.67, N
9.27; found: C 54.99, H 7.83, N 10.01.
D-C8Br. Yield: 91.0%. H NMR (298 K, 250 MHz, DMSO-d6)
d ¼ 9.3 (s, 2H), 7.86 (d, 4H), 5.32 (s, 4H), 4.19 (t, 4H), 1.80 (d, 4H),
A-C10Br. Yield: 84%. 1H NMR (298 K, 250 MHz, DMSO-d6)
d ¼ 9.37 (m, 2H), 7.83 (m, 4H), 4.16 (m, 8H), 2.10 (s, 8H), 1.25
(m, 34H), 0.86 (t, 6H).
1.24 (s, 18H), 0.84 (t, 6H).
Elemental analysis (%) calcd for D-C8Br: C 54.55, H 7.75, N
9.79; found: 54.12, H 7.09, N 10.12.
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Elemental analysis (%) calcd for A-C10Br: C 58.09, H 9.29, N
8.47; found: C 57.47, H 9.29, N 8.99.
D-C10Br. Yield: 81.7%. H NMR (298 K, 250 MHz, DMSO-d6)
d ¼ 9.31 (s, 2H), 7.87 (d, 4H), 5.32 (s, 4H), 4.20 (t, 4H), 1.81 (d,
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A-C12Br. Yield: 90.3%. H NMR (298 K, 250 MHz, DMSO-d6)
4H), 1.23 (s, 28H), 0.87 (t, 6H).
d ¼ 9.23 (m, 2H), 7.79 (m, 4H), 4.14 (m, 8H), 1.77 (s, 8H), 1.22
Elemental analysis (%) calcd for D-C10Br: C 57.32, H 8.34, N
8.91; found: C 59.11, H 7.99, N 8.95.
D-C12Br. Yield: 96.2%. H NMR (298 K, 250 MHz, DMSO-d6)
(m, 40H), 0.84 (t, 6H).
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Elemental analysis (%) calcd for A-C12Br: C 60.31, H 9.56, N
7.82; found: C 60.00, H 9.45, N 7.99.
d ¼ 9.37 (s, 2H), 7.85 (d, 4H), 5.30 (s, 4H), 4.19 (t, 4H), 1.79 (d,
B-C4Br. Yield: 86.0%. 1H NMR (298 K, 250 MHz, DMSO-d6) d ¼
9.27 (s, 2H), 7.80 (d, 2H), 7.77–7.70 (m, 2H), 4.44–4.30 (m, 4H), 4.20
(t, 4H), 3.79 (t, 4H), 1.85–1.68 (m, 4H), 1.26 (dd, 4H), 0.90 (t, 6H).
Elemental analysis (%) calcd for B-C4Br: C 45.02, H 6.67, N
11.67, O 3.33; found: C 45.3, H 7.1, N 10.7, O 2.8.
4H), 1.20 (s, 38H), 0.88 (t, 6H).
Elemental analysis (%) calcd for D-C12Br: C 59.64, H 8.83, N
8.18; found: C 58.99, H 8.01, N 7.99.
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2.3. Synthesis of bis(dodecyl)-1,1-(oxydi-2,1-ethane-diyl)bis-
imidazolium (B-C12) with several anion derivatives A, with
A ¼ BF4, ClO4, PF6, NTf2
B-C8Br. Yield: 76.5%. H NMR (298 K, 250 MHz, DMSO-d6)
d ¼ 9.33 (s, 2H), 7.81 (s, 2H), 7.75 (s, 2H), 4.38 (t, 4H), 4.20 (t,
4H), 3.79 (t, 4H), 1.90–1.64 (m, 4H), 1.24 (s, 20H), 0.85 (t, 6H).
Elemental analysis (%) calcd for B-C8Br: C 52.9, H 8.1, N 9.5;
Synthesis of bis(n-dodecyl)-1,1-(oxydi-2,1-ethane-diyl)bis-
found: C 52.64, H 8.28, N 9.79.
imidazolium tetrauoroborate [B-C12][BF4]2. To a solution of
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B-C10Br. Yield: 93.6%. H NMR (298 K, 250 MHz, DMSO-d6) bis(dodecyl)-1,1-(oxydi-2,1-ethanediyl)bisimidazolium bromide
d ¼ 9.18 (s, 2H), 7.79 (d, 2H), 7.70 (d, 2H), 4.35 (t, 4H), 4.17 (0.5 g, 0.71 mmol) in water (20 mL) was added NaBF4 (0.19 g,
(t, 4H), 3.77 (t, 4H), 1.76 (m, 4H), 1.24 (s, 28H), 0.85 (t, 6H).
1.77 mmol). The mixture was stirred for 2 days, followed by
Elemental analysis (%) calcd for B-C10Br: C 55.6, H 8.6, extraction with CH2Cl2 (10 mL, three times). The organic phase
N 8.6, O 2.5; found C 56.3, H 9.1, N 7.9, O 2.0.
was washed with water. The solution was evaporated to dryness
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B-C12Br. Yield: 87.2%. H NMR (298 K, 250 MHz, DMSO-d6) to give bis(dodecyl)-1,1-(oxydi-2,1-ethanediyl)bisimidazolium
d ¼ 9.14 (s, 2H), 7.78 (d, 2H), 7.69 (d, 2H), 4.35 (t, 4H), 4.16 (t, tetrauoroborate. 1H NMR (298 K, 200 MHz, DMSO-d6) d ¼ 9.07
4H), 3.77 (t, 4H), 1.78 (m, 4H), 1.24 (s, 36H), 0.85 (t, 6H).
(s, 2H), 7.79 (d, 2H), 7.70 (d, 2H), 4.36 (t, 4H), 4.18 (t, 4H), 3.80 (t,
Elemental analysis (%) calcd for B-C12Br: C 57.97, H 9.09, 4H), 1.80 (m, 4H), 1.27 (s, 36H), 0.87 (t, 6H).
N 7.96, O 2.27; found: C 58.32, H 9.21, N 7.76, O 2.07.
Elemental analysis (%) calcd: C 65.7, H 10.1, N 7.98; found: C
C-C4Br. Yield: 90%. 1H NMR (298 K, 250 MHz, DMSO-d6) 64.39, H 9.97, N 7.92.
d ¼ 9.27 (s, 2H), 7.79 (d, 4H), 7.40 (m, 4H), 5.41 (m, 4H), 4.20
Synthesis of bis(n-dodecyl)-1,1-(oxydi-2,1-ethane-diyl)bis-
imidazolium perchlorate [B-C12][ClO4]2. NaClO4 (0.384 g, 3.1
(t, 4H), 1.85–1.71 (m, 4H), 1.26 (dd, 4H), 0.88 (t, 6H).
Elemental analysis (%) calcd for C-C4Br: C 51.58, H 6.30, mmol) was added to a solution of bis(dodecyl)-1,1-(oxydi-2,1-
N 10.94; found: 52.36, H 5.99, N 10.71. ethanediyl)bisimidazolium bromide (1.0 g, 1.4 mmol) in 10 mL
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C-C8Br. Yield: 86.5%. H NMR (298 K, 250 MHz, DMSO-d6) dichloromethane and stirred for 2 days. The suspension was
d ¼ 9.33 (s, 2H), 7.78 (d, 4H), 7.40 (s, 4H), 5.43 (s, 4H), 4.20 ltered to remove the precipitated bromide salt and the organic
(t, 4H), 1.24 (s, 24H), 0.84 (t, 6H).
phase was washed with small volumes of cold water to ensure
Elemental analysis (%) calcd for C-C8Br: C 57.69, H 7.75, complete removal of the bromide salt. The solvent was removed
N 8.97; found: C: 57.08, H 7.86, N 8.73.
under vacuum and the resulting ionic liquid was dried at room
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C-C10Br. Yield: 93.6%. H NMR (298 K, 250 MHz, DMSO-d6) temperature under dynamic vacuum for 24 h. 1H NMR (298 K, 250
d ¼ 9.35 (t, 2H), 7.79 (d, 4H), 7.40 (s, 4H), 5.40 (s, 4H), 4.14 MHz, DMSO-d6) d ¼ 9.07 (s, 2H), 7.77 (d, 2H), 7.66 (d, 2H), 4.34 (t,
(t, 4H), 1.24 (s, 32H), 0.85 (t, 6H),
Elemental analysis (%) calcd for C-C10Br: C 60.00, H 8.29,
N 8.23; found: C 59.56, H 9.10, N 8.75.
4H), 4.15 (t, 4H), 3.78 (t, 4H), 1.78 (m, 4H), 1.24 (s, 36H), 0.86 (t, 6H).
Elemental analysis (%) calcd: C 55.0, H 8.6, N 7.5; found: C
55.5, H 7.05, N 7.75.
This journal is © The Royal Society of Chemistry 2014
J. Mater. Chem. C, 2014, 2, 458–473 | 461