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1H), 7.14-7.26 (m, 3H). 13C NMR (125 MHz, DMSO-d6) δ ppm:
164.14, 162.17, 151.44, 142.96, 137.54, 136.79, 131.89,
130.55, 129.39, 128.00, 126.86, 123.83, 123.23, 119.83,
116.01, 115.84, 110.91.
C NMR (125 MHz, CD2Cl2) δ ppm: 184.99, 163.72, 161.81 –
DOI: 10.1039/C6NJ03634A
13
161.56, 158.81, 156.73, 152.80, 138.98 , 137.13, 136.13,
128.85, 128.64, 126.87, 123.85, 123.17, 118.55 , 116.31,
115.43, 111.08, 100.65, 96.33, 96.11, 95.90, 52.96, 52.74 ,
52.52, 52.31, 27.30.MS (APCI, M+H+) for 2F-Ir, Exact mass:
902.19; Obtained mass: 903.19.
2-(2,4-difluorophenyl)-1-phenyl-1H-benzo[d]imidazole
(2F).
White crystal. Yield: 54%. M.p: 136.9-138.3
℃
. 1H NMR (500
MHz, CDCl3) δ ppm: 7.71 (s, 2H), 7.50 (d, J = 7.8 Hz, 4H), 7.29
(dd, J = 7.6, 10.0 Hz, 4H), 7.10 (t, J = 7.3 Hz, 2H). 13C NMR (125
MHz, CDCl3) δ ppm: 168.63, 137.92, 128.96, 124.35, 120.04,
24.48.
3F-Ir. Yellow-green solid. Yield: 48%. 1H NMR (500 MHz, CD2Cl2)
δ ppm: 7.98 (s, 6H), 7.86 (dd, J = 15.2, 6.6 Hz, 4H), 7.78 (s, 2H),
7.57 (s, 4H), 7.36 (d, J = 7.1 Hz, 2H), 6.46-6.72 (m, 2H), 5.63 (s,
1H), 2.14 (s, 6H). 13C NMR (125 MHz, CD2Cl2) δ ppm: 185.44,
140.84, 136.09, 134.76, 130.80-130.49, 128.27, 124.22,
123.70, 116.23, 110.85, 109.23, 101.38, 53.59, 53.37, 53.15,
52.94, 27.85. MS (APCI, M+H+) for 3F-Ir, Exact mass: 938.17;
Obtained mass: 939.17.
2-(3,4,5-trifluorophenyl)-1-phenyl-1H-benzo[d]imidazole
Yellowish-brown needle crystal. Yield: 46%. M.p: 161.1-162.3
. 1H NMR (500 MHz, CDCl3) δ ppm: 7.89 (d, J = 7.9 Hz, 1H),
(3F).
℃
7.58 (d, J = 5.6 Hz, 3H), 7.38 (t, J = 7.5 Hz, 1H), 7.32 (t, J = 9.3
Hz, 3H), 7.24 (t, J = 7.5 Hz, 3H). 13C NMR (125 MHz, CDCl3) δ
ppm: 151.96, 149.97, 148.86, 142.41, 141.64, 139.60, 137.40
(s, 15H), 136.21, 130.33, 130.13, 129.48, 127.46, 125.92,
124.18, 123.57, 120.02, 113.68, 110.66.
0F-Ir. Yellow-green solid. Yield: 45%. 1H NMR (500 MHz, CD2Cl2)
δ ppm: 7.73 (d, J = 6.4 Hz, 10H), 7.65 (s, 2H), 7.37 (s, 4H), 7.21
(s, 2H), 6.65 (d, J = 7.0 Hz, 2H), 6.59 (dd, J = 15.4, 7.0 Hz, 4H),
6.52 (d, J = 6.9 Hz, 2H), 5.41 (s, 1H), 1.95 (s, 6H). 13C NMR (125
MHz, CD2Cl2) δ ppm: 184.49, 163.13, 148.65, 139.65, 136.06,
134.86, 134.33, 129.70, 129.41, 128.06, 127.68, 124.47,
123.34, 122.52, 119.34, 115.70, 110.02, 100.41, 52.96, 52.74,
52.52, 52.31, 27.34. MS (APCI, M+H+) for 0F-Ir, Exact mass:
830.22; Obtained mass: 831.23.
1,2-diphenyl-1H-benzo[d]imidazole (0F). Yellow powder. Yield:
1
53%. M.p: 108.7-109.6
℃
. H NMR (500 MHz, CDCl3) δ ppm:
7.94 (d, J = 7.9 Hz, 1H), 7.60 (d, J = 7.5 Hz, 2H), 7.57-7.48 (m,
3H), 7.37 (d, J = 6.8 Hz, 2H), 7.33 (d, J = 7.1 Hz, 4H), 7.29 (d, J =
11.4 Hz, 2H). 13C NMR (125 MHz, CDCl3) δ ppm: 152.13, 136.99,
136.78, 129.93, 129.71, 129.54, 128.73, 128.37, 127.43,
123.60, 123.30, 119.64, 110.56.
Acknowledgements
General syntheses of the Ir(III) complexes
Authors gratefully acknowledge the supports from the
National Natural Science Foundation of China (Grant No.
61204021), Liaoning Provincial Natural Science Foundation
(Grant No. 2015020651), Talents training project of USTL
(Grant No. 2014RC01) and Innovation team construction
project of USTL (Grant No. 2015TD02).
Under N2 atmosphere, a mixture of C^N ligand (2.0 mmol),
IrCl3·3H2O (1.0 mmol), 2-ethoxyethanol and water (16 mL, 3:1,
v/v) were heated to 110~120
℃for 24 h. Then the reaction
mixture was cooled to RT and water was added. The yellow
dimer was obtained after vacuum filtration and drying. The
dimer is used directly for the next step without further
treatment. Subsequently, a mixture of the above resulting
dimer, acetylacetone (2.0 mmol), potassium carbonate (5.0
References
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mmol) and 2-ethoxyethanol 12 mL was heated to 110~120
℃
,
for 24 h under N2 atmosphere. After cooling the mixture to RT
and the addition of water, the resulting precipitate was
collected by vacuum filtration and drying. The yellow product
was obtained by column chromatography on silica gel using
petroleum and ethyl acetate as eluents.
2
3
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1F-Ir. Jade green solid. Yield: 51%. H NMR (500 MHz, CD2Cl2)
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δ
ppm: 7.76 (s, 6H), 7.69 (d, J = 5.4 Hz, 6H), 7.38 (s, 4H), 7.22
(s, 2H), 6.60-6.71 (m, 2H), 6.32 (t, J = 8.3 Hz, 2H), 6.17 (d, J =
9.6 Hz, 2H), 5.41 (s, 1H), 1.95 (s, 6H). 13C NMR (125 MHz,
8
9
CD2Cl2)
δ ppm: 185.32, 163.55, 162.81, 161.53, 152.60,
Y. You, S. Y. Park, Dalton Trans., 2009, 1267.
139.99 , 136.59, 135.19, 131.80, 130.48, 130.23, 128.30,
126.60, 124.18, 123.36 , 120.90, 116.06, 110.80, 107.45,
107.27, 101.19, 53.60, 53.38, 53.17, 52.95, 27.94. MS (APCI,
M+H+) for 1F-Ir, Exact mass: 866.20; Obtained mass: 867.21.
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2F-Ir. Jade green solid. Yield: 47%. 1H NMR (500 MHz, CD2Cl2)
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δ
7.66 (s, 8H), 7.57 (s, 1H), 7.39 (s, 4H), 7.20 (s, 2H), 6.18 (t, J
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