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Y. Wang et al. / Tetrahedron 66 (2010) 1483–1488
sulfate. The solvent was removed by rotary evaporation and gain
References and notes
Tfl-picH (0.93 g, 95.0%) as a white solid. 1H NMR (CDCl3, 400 MHz),
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4.8. Synthesis of (Piq)2Ir(Tfl-pic)
To a mixture of IrCl3$3H2O (0.3 g, 0.85 mmol) and water (5 mL)
was added 1-phenylisoquinoline (0.5 g, 2.44 mmol) and 2-ethoxy-
ethanol (15 mL). The mixture was refluxed under inert gas atmo-
sphere for 20 h. After cooled, the colored precipitate was filtered off
and was washed with water, followed by hexane. Then gain a red
solid (0.42 g, 78.0%). A mixture of [(C^N)2IrCl]2 dimmers (0.2 g,
0.16 mmol), compound Tfl-picH (0.5 g, 0.4 mmol), and
85–90 mg of sodium carbonate were refluxed under inert gas at-
mosphere in 2-ethoxyethanol for 12–15 h. After cooling to room
temperature, extracted with DCM and the combined organic layer
was dried over anhydrous magnesium sulfate. The crude product
was purified by dry flash silica gel column with DCM to gain the
goal product (0.28 g, 53.0%) as a red solid. 1H NMR (CDCl3,
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400 MHz),
d
(ppm): 8.95–8.92 (1H, d, J¼8.4 Hz), 8.82–8.80 (1H, d,
J¼9.52 Hz), 8.62–8.60 (1H, d, J¼6.4 Hz), 8.12–8.10 (1H, d, J¼7.6 Hz),
8.04–8.03 (1H, d, J¼7.2 Hz), 7.94–7.92 (1H, d, J¼7.2 Hz), 7.83–7.57
(23H, m), 7.36–7.34 (6H, d, J¼7.2 Hz), 7.15–7.14 (1H, d, J¼6.4 Hz),
6.89–6.86 (1H, t), 6.66–6.61 (2H, t), 6.58–6.56 (1H, d, J¼8.0 Hz),
6.46–6.42 (1H, t), 6.3–6.28 (1H, d, J¼8.0 Hz), 6.17–6.15 (1H, d,
J¼7.2 Hz), 4.27–4.26 (2H, t), 2.07–2.0 (12H, t), 1.26–1.06 (56H, m),
0.81–0.68 (27H, m). Anal. Calcd for C121H140IrN3O3: C 77.44, H 7.52,
N 2.24. Found: C 78.94, H 7.60, N 2.34%. TOF-MS (MþNaþ): 1890.
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4.9. Synthesis of and (Piq)2Ir(Brfl-pic)
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It was prepared according to the synthetic procedure of
(Piq)2Ir(Tfl-pic). A red solid was obtained with a yield of 56.0%. 1H
NMR (CDCl3, 400 MHz), 8.97–8.95 (1H, m), 8.86–8.84 (1H, d,
J¼9.6 Hz), 8.64–8.62 (1H, d, J¼6.4 Hz), 8.14–8.12 (1H, d, J¼8.4 Hz),
8.10–8.08 (1H, d, J¼7.6 Hz), 7.97–7.95 (1H, d, J¼7.6 Hz), 7.84–7.77
(3H, m), 7.72–7.60 (6H, m), 7.53–7.50 (2H, m), 7.46–7.42 (4H, m),
7.37–7.36 (1H, d, J¼6.4 Hz), 7.20–7.18 (1H, d, J¼6.4 Hz), 6.91–6.81
(1H, t), 6.70–6.62 (3H, m), 6.48–6.44 (1H, t), 6.33–6.31 (1H, d,
J¼7.6 Hz), 6.18–6.16 (1H, d, J¼7.6 Hz), 4.28–4.25 (2H, t), 1.94–1.89
(4H, m), 1.62–1.57 (2H, m), 1.25–1.04 (14H, m), 0.84–0.81 (3H, t),
0.59–0.58 (4H, m). Anal. Calcd. For C62H56Br2IrN3O3: C 59.90, H
4.54, N 3.38. Found: C 60.73, H 4.94, N 3.30%.
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Financial support from the National Natural Science Foundation
of China (20772101), the Science Foundation of Human Province
(2009FJ2002 and 2007FJ3017) and the Postgraduate Science
Foundation for Innovation in Human Province (CX2009B124 and
S2008 yjscx09).
Supplementary data
TGA thermogram graph, DSC traces and atomic force micro-
scope images for the (Piq)2Ir(Tfl-pic) and (Piq)2Ir(Brfl-pic) com-
plexes were provided. Supplementary data associated with this