L. Douce et al.
FULL PAPER
(300 MHz, CDCl3, 20 °C): δ = 9.59 (t, 4J = 1.65 Hz, N–CH–N
added to a small Schlenk tube under an atmosphere of nitrogen.
Dioxane (3 mL) and the aryl halide (1 mmol) were then added, and
imidazolium), 7.67 (d, 4J = 1.60 Hz, 2 H, N–CH–CH–N imid-
3
azolium), 7.64 (m, J = 9.0 Hz, 2 H, aromatic, AAЈ system), 7.01 the mixture was heated in an oil bath at 80 °C. At the conclusion
3
3
(m, J = 9.0 Hz, 2 H, aromatic, BBЈ system), 3.95 (t, J = 6.6 Hz,
of the reaction, the reaction mixture was cooled and analysed by
2 H, CH2–O), 1.79 (m, 2 H, CH2–CH2–O), 1.43 (m, 2 H, CH2– GC–MS.
3
CH2–CH2–O), 1.28 (br. s, 32 H, aliphatic), 0.89 (t, J = 7.0 Hz, 3
Carrier Mobility Measurements: The charge carrier mobility in the
H, CH3) ppm. 13C NMR (75 MHz, CDCl3, 20 °C): δ = 14.10
(–CH3), 22.69, 25.97, 29.10, 29.36, 29.41, 29.60, 29.63, 29.65, 29.68,
31.92, 68.65 (O–CH2), 120.68 (q, J = 320 Hz, CF3), 122.02, 123.44,
mesophase was measured by TOF (time-of-flight) measurement ap-
paratus equipped with a polarising microscope and a hot stage.
The light source was a pulsed nitrogen gas laser (Nippon Laser, λ
= 337 nm, 0.8 ns). The cells consisting of ITO- and TiO2-coated
glasses for an asymmetric structure of sandwich-type cells were
mounted on the hot stage and electric bias was applied by a stabi-
lised DC power supply. The resulting photocurrent was detected
with a digital oscilloscope with a homemade preamplifier.
126.86, 132.40, 160.64 ppm. IR (KBr pellet): ν = 3141 and 3102
˜
(C–H aromatic), 2917 and 2852 (C–H aliphatic), 1555 and 1513
(C=N imidazolium), 1266 (OTf–) cm–1. λ (ε) = 276 (18400) nm.
C40H61F3N2O5S (738.98): calcd. C 65.01, H 8.32, N 3.79, S 4.34;
found C 64.78, H 8.58, N 4.25, S 3.56.
1,3-Bis(4-tetradecyloxyphenyl)-3H-imidazol-1-ium Trifluorometh-
X-ray Crystallography: The selected crystal was mounted on a
Nonius Kappa-CCD area detector diffractometer (Mo-Kα, λ =
0.71073 Å). The complete conditions of data collection (Denzo
software) and structure refinements are given below. The cell pa-
rameters were determined from reflections taken from one set of
ten frames (1.0° steps in phi angle), each at 20 s exposure. The
structures were solved by direct methods (SHELXS97) and refined
against F2 using the SHELXL97 software. All non-hydrogen atoms
were refined anisotropically. Hydrogen atoms were generated ac-
cording to stereochemistry and refined by using a riding model in
SHELXL97.[20] CCDC-628899 contains the supplementary crystal-
lographic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif. Colourless single crystal;
crystal dimension: 0.10ϫ0.08ϫ0.05 mm3. C70H104I2N4O4Pd, M =
1
anesulfonate (1d): Yield crystalline solid (0.479 g; 58%). H NMR
(300 MHz, CDCl3, 20 °C): δ = 9.64 (t, 4J = 1.74 Hz, N–CH–N
imidazolium), 7.66 (d, 4J = 1.70 Hz, 2 H, N–CH–CH–N imid-
3
azolium), 7.64 (m, J = 7.02 Hz, 2 H, aromatic, AAЈ system), 7.03
(m, 3J = 6.99 Hz, 2 H, aromatic, BBЈ system), 3.97 (t, 3J = 6.57 Hz,
2 H, CH2–O), 1.80 (m, 2 H, CH2–CH2–O), 1.43 (m, 2 H, CH2–
3
CH2–CH2–O), 1.27 (br. s, 40 H, aliphatic), 0.88 (t, J = 7.02 Hz, 3
H, CH ) ppm. IR (KBr pellet): ν = 3143 and 3101 (C–H aromatic),
˜
3
2917 and 2850 (C–H aliphatic), 1555 and 1513 (C=N imidazolium),
1265 (OTf–) cm–1. λ (ε) = 277 (27047) nm. C44H69F3N2O5S
(795.09): calcd. C 66.47, H 8.75, N 3.52, S 4.03; found C 66.35, H
8.77, N 3.48, S 4.17.
1,3-Bis(4-hexadecyloxyphenyl)-3H-imidazol-1-ium Trifluorometh-
1
anesulfonate (1e): Yield crystalline solid (0.376 g; 34%). H NMR
¯
(300 MHz, CDCl3, 20 °C): δ = 9.72 (t, 4J = 1.53 Hz, N–CH–N
imidazolium), 7.65 (d, 4J = 1.53 Hz, 2 H, N–CH–CH–N imid-
1425.77 g/mol; Triclinic; space group P1; a = 10.7060(1) Å; b =
15.8080(2) Å; c = 21.6950(3) Å; Z = 2; Dcalcd. = 1.354 g/cm; µ (Mo-
Kα) = 1.195 mm–1; a total of 20389 reflections; 1.34 °ϽθϽ30.06°,
1842 independent reflections with 12376 having IϾ2σ(I); 730 pa-
rameters; Final results: R1 = 0.0460; wR2 = 0.1287, Goof = 0.996,
maximum residual electronic density = 1.887 e/Å3.
3
azolium), 7.67 (m, J = 7.03 Hz, 2 H, aromatic, AAЈ system), 7.03
(m, 3J = 7.0 Hz, 2 H, aromatic, BBЈ system), 3.99 (t, 3J = 6.57 Hz,
2 H, CH2–O), 1.81 (m, 2 H, CH2–CH2–O), 1.41 (m, 2 H, CH2–
3
CH2–CH2–O), 1.27 (br. s, 40 H, aliphatic), 0.89 (t, J = 7.0 Hz, 3
H, CH3) ppm. 13C NMR (75 MHz, CDCl3, 20 °C): δ = 14.06
(–CH3), 22.64, 25.91, 29.02, 29.31 29.53, 29.60, 29.57, 29.66, 31.87,
68.65 (O–CH2), 116.05, 121.82, 123, 126.78, 132.26, 160.80 ppm.
Acknowledgments
IR (KBr pellet): ν = 3141 and 3102 (C–H aromatic), 2918 and 2852
˜
We are especially grateful to D. Guillon and J. Harrowfield for the
critical evaluation of this manuscript, we also thank A. De Cian
for the X-ray diffraction studies. This work was supported by the
Institut for Physics and Chemistry of Materials Strasbourg
(I. P. C. M. S), the Institut of Chemistry and Louis Pasteur Univer-
sity.
(C–H aliphatic), 1555 and 1513 (C=N imidazolium), 1266 (OTf–)
cm–1. λ (ε) = 277 (18438) nm. C48H77F3N2O5S (851.20): calcd. C
67.73, H 9.12, N 3.29; found: C 67.75, H 8.98, N 3.39.
Palladium–Carbene Complex 2: Compound 1b (250.0 mg,
0.367 mmol), Pd(OAc)2 (41.2 mg, 0.183 mmol) and NaI (55.0 mg,
0.367 mmol) were suspended in THF (15 mL). tBuOK (41.1 mg,
0.367 mmol) was added to the suspension under an atmosphere of
nitrogen. The resulting solution was stirred for 1.5 d at 40 °C. After
evaporation of the solvent, the residue was extracted with dichloro-
methane/water. After drying the DCM layer over Na2SO4 and
evaporating it to dryness, the orange solid was purified by flash
column chromatography (SiO2, CH2Cl2/pentane). Yield: 116 mg,
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1
44%. H NMR (300 MHz, CDCl3): δ = 7.51 (d, J = 8.9 Hz, 4 H),
6.96 (s, 2 H), 6.75 (d, J = 8.9 Hz, 4 H), 4.05 (t, J = 6.6 Hz, 4 H),
1.86 (m, 4 H), 1.53–1.26 (m, 28 H), 0.89 (t, J = 6.7 Hz, 6 H) ppm.
13C NMR (75 MHz, CDCl3): δ = 167.0 (Ccarbene), 158.5 (Cq), 133.0
(Cq), 127.8 (CH), 123.8 (CH), 114.5 (CH), 68.2, 31.9, 29.7, 29.6,
29.5, 29.4, 29.3, 26.2, 22.7, 14.1 (CH3) ppm. C71H105I2N3O4Pd
(1424.84): calcd. C 59.0, H 7.3, N 3.9; found C 58.95, H 7.45, N
3.80.
General Procedure for the Suzuki-Type Coupling Reactions: Palla-
dium acetate (1–2.5 mol-%), imidazolium salt (2–5 mol-%), Cs2CO3
(652 mg, 2 mmol) and phenylboronic acid (183 mg, 1.5 mmol) were
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3904
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Eur. J. Inorg. Chem. 2007, 3899–3905