1
LG2′: (Yield: 75%). H NMR (δ (ppm), CDCl3, 400 MHz):
2.51 (br), 2.47 (s, 3H), 2.25 (t, J = 6.4 Hz, 2H), 2.03–1.96 (m,
2H). 13C NMR (δ (ppm), CDCl3, 100.65 MHz): 177.85, 167.71,
167.52, 159.71, 156.58, 155.81, 154.98, 151.82, 150.81, 150.71,
149.84, 149.40, 149.14, 148.16, 147.87, 143.37, 143.18, 140.58,
140.37, 140.16, 140.14, 139.53, 131.67, 131.59, 130.61, 130.48,
128.34, 126.87, 126.11, 124.63, 124.58, 124.39, 124.20, 123.56,
122.28, 122.23, 121.22, 120.87, 120.42, 120.38, 117.05, 116.92,
109.94, 109.55, 107.38, 107.35, 101.90, 101.87, 73.10, 69.82,
69.11, 36.43, 34.97, 26.57, 21.41. MALDI-TOF-MS: m/z
2742.3 [M]+.
8.67 (d, J = 4.0 Hz, 1H), 8.13 (d, J = 7.6 Hz, 7H), 7.76 (s, 6H),
7.61 (d, J = 8.4 Hz, 1H), 7.51–7.49 (m, 8H), 7.43–7.30 (m,
10H), 7.30–7.25 (m, 11H), 6.74 (d, J = 2.0 Hz, 2H), 6.68 (t, J =
2.0 Hz, 1H), 5.31 (s, 4H), 4.60 (s, 2H), 4.57 (s, 2H).
General synthetic route for IrLGn (n = 0–3) and IrLGn′ (n = 0–2)
IrCl3·3H2O and 2.5 equiv. of cyclometalating ligand (LGn or
L
Gn′) were added into a mixture of 2-methoxyethanol and water
1
(3 : 1, v/v), and the reaction mixture was refluxed for 36 h to
yield the corresponding dichloro-bridged dimer complexes.
After cooling to room temperature, the solution was filtered
through Celite and the yellow precipitate was washed with water,
ether and hexane and dried in vacuo. The obtained dimer and 2.2
equiv. of bipy-COOH were added to CH2Cl2 (CH2Cl2/methanol
for IrLG0 and IrLG0′), and the reaction mixture was refluxed
under an inert atmosphere for 24 h. After cooling to room temp-
erature, the crude product was purified by silica gel column
chromatography with CH2Cl2/methanol (various ratios based on
the mixture properties) eluent to give the pure product. Yield:
84–20%.
IrLG3: (Yield: 20%). H NMR (δ (ppm), CDCl3, 400 MHz):
8.74 (d, J = 3.2 Hz, 2H), 8.02 (d, J = 8.0 Hz, 31H), 7.73–7.17
(m, 129H), 6.96 (d, J = 5.2 Hz, 1H), 6.87–6.50 (m, 26H), 6.91
(m, 2H), 5.17 (s, 16H), 4.89 (s, 8H), 4.46 (s, 4H), 4.40 (s, 4H),
2.85 (t, J = 6.0 Hz, 2H), 2.42 (s, 3H), 2.37 (br), 2.30 (t, J = 6.4
Hz, 2H), 2.98–1.96 (m, 2H). 13C NMR (δ (ppm), CDCl3,
100.65 MHz): 177.23, 167.72, 167.44, 160.00, 159.62, 156.03,
155.69, 155.27, 151.96, 150.92, 149.97, 149.48, 149.11, 148.27,
147.94, 143.55, 143.32, 140.68, 140.39, 139.82, 139.78, 139.53,
139.04, 131.84, 131.67, 130.62, 130.45, 128.76, 128.45, 128.28,
126.88, 126.15, 125.31, 124.70, 124.29, 124.13, 123.59, 123.28,
123.14, 122.27, 121.33, 120.91, 120.41, 120.39, 116.96, 116.77,
113.12, 111.06, 109.60, 106.91, 102.02, 101.47, 73.11, 69.80,
69.73, 69.08, 35.63, 34.93, 26.16, 21.40. MALDI-TOF-MS: m/z
4917.0 [M]+.
1
IrLG0: (Yield: 84%). H NMR (δ (ppm), CDCl3, 400 MHz):
8.85–8.84 (m, 2H), 7.74–7.63 (m, 6H), 7.34–7.32 (m, 2H), 7.23
(d, J = 5.6 Hz, 2H), 7.17 (d, J = 5.6 Hz, 1H), 7.00 (t, J = 7.6 Hz,
2H), 6.90–6.86 (m, 3H), 6.82 (d, J = 6.0 Hz, 1H), 6.32–6.29 (m,
1H), 4.28 (br), 2.94 (t, J = 7.2 Hz, 2H), 2.62 (s, 3H), 2.51 (d, J
= 5.6 Hz, 6H), 2.42–2.33 (m, 2H), 2.10–2.04 (m, 2H). 13C
NMR (δ (ppm), CDCl3, 100.65 MHz): 177.42, 167.30, 167.04,
156.02, 155.81, 155.42, 151.94, 150.96, 150.88, 149.66, 149.58,
149.23, 148.00, 147.71, 143.67, 143.49, 131.86, 131.76, 130.46,
130.33, 128.49, 128.26, 126.32, 125.98, 124.47, 124.42, 124.35,
124.18, 122.26, 122.19, 120.24, 120.07, 35.65, 34.92, 26.32,
21.50, 21.37, 21.34. TOF-MS (ESI): Calcd. for [M−Cl]+
785.2468; found, 785.2461.
1
IrLG0′: (Yield: 83%). H NMR (δ (ppm), CDCl3, 400 MHz):
8.77 (d, J = 7.8 Hz, 2H), 7.86–7.82 (m, 2H), 7.74–7.69 (m, 4H),
7.55 (d, J = 8.0 Hz, 2H), 7.47–7.44 (m, 2H), 7.25–7.23 (m, H),
7.20–7.18 (m, H), 7.02–6.94 (m, 2H), 6.84–6.82 (m, 2H), 6.08
(s, 2H), 3.30 (br), 2.94 (t, J = 7.2 Hz, 2H), 2.60 (s, 3H),
2.35–2.28 (m, 2H), 2.12 (s, 6H), 2.09–2.04 (m, 2H). 13C NMR
(δ (ppm), CDCl3, 100.65 MHz): 177.95, 167.80, 167.68,
156.21, 155.59, 155.25, 151.84, 150.77, 149.33, 148.29, 148.14,
140.80, 140.72, 140.66, 137.74, 137.70, 132.40, 132.36, 128.56,
128.20, 125.92, 125.55, 124.50, 124.46, 123.46, 123.42, 122.63,
122.49, 119.07, 118.96, 35.96, 34.80, 26.45, 21.71, 21.38.
TOF-MS (ESI): Calcd. for [M−Cl]+ 785.2468; found, 785.2475.
1
IrLG1: (Yield: 71%). H NMR (δ (ppm), CDCl3, 400 MHz):
8.74 (s, 1H), 8.64 (s, 1H), 8.15 (d, J = 7.6 Hz, 8H), 7.93 (s, 2H),
7.79 (t, J = 2.0 Hz, 2H), 7.73 (d, J = 2.0 Hz, 4H), 7.68 (d, J =
5.6 Hz, 2H), 7.60–7.57 (m, 2H), 7.54 (d, J = 8.0 Hz, 8H),
7.44–7.40 (m, 10H), 7.33–7.29 (m, 8H), 7.16 (d, J = 5.6 Hz,
1H), 7.07 (d, J = 5.6 Hz, 1H), 7.03 (d, J = 6.0 Hz, 1H), 6.98 (d,
J = 6.0 Hz, 1H), 6.94–6.88 (m, 2H), 6.86–6.80 (m, 2H), 6.29 (t,
J = 1.2 Hz, 1H), 6.27 (t, J = 1.2 Hz, 1H), 4.92–4.81 (m, 8H),
2.90 (t, J = 6.8 Hz, 2H), 2.75 (br), 2.54 (s, 3H), 2.26 (t, J = 6.0
Hz, 2H), 2.07–2.00 (m, 2H). 13C NMR (δ (ppm), CDCl3,
100.65 MHz): 177.81, 167.96, 167.79, 156.69, 155.87, 155.03,
151.88, 150.85, 150.75, 149.51, 149.27, 148.35, 148.07, 143.34,
143.14, 141.40, 141.38, 140.43, 139.61, 131.77, 131.68, 130.76,
130.64, 128.48, 126.19, 124.79, 124.50, 124.31, 123.61, 122.45,
122.39, 121.19, 120.84, 120.50, 120.45, 116.88, 116.73, 109.56,
72.41, 70.51, 36.52, 35.05, 26.64, 21.49. MALDI-TOF-MS: m/z
1657.7 [M−Cl]+.
1
IrLG1′: (Yield: 60%). H NMR (δ (ppm), CDCl3, 400 MHz):
8.96 (s, 1H), 8.79 (s, 1H), 8.18 (d, J = 8.0 Hz, 8H), 7.73–7.72
(m, 2H), 7.60–7.58 (m, 2H), 7.52–7.42 (m, 20H), 7.35–7.31 (m,
10H), 7.07 (d, J = 5.2 Hz, 1H), 6.98 (d, J = 5.6 Hz, 1H),
6.88–6.64 (m, 9H), 6.49 (t, J = 6.8 Hz, 1H), 6.19 (s, 2H),
4.61–4.34 (m, 8H), 2.94 (br), 2.85 (t, J = 6.0 Hz, 2H), 2.55–2.41
(m, 5H), 2.07–2.04 (m, 2H). 13C NMR (δ (ppm), CDCl3,
100.65 MHz): 176.73, 167.09, 166.71, 155.55, 155.41, 155.36,
152.15, 150.84, 150.78, 149.55, 149.09, 148.17, 143.06, 142.84,
142.47, 142.41, 140.53, 140.51, 139.49, 139.19, 139.16, 137.66,
130.21, 129.94, 128.45, 128.16, 126.28, 126.01, 124.62, 124.35,
123.28, 122.80, 121.69, 120.59, 120.55, 120.50, 120.47, 119.12,
118.89, 109.78, 109.73, 72.69, 71.21, 34.84, 30.96, 25.74,
21.43. TOF-MS (ESI): Calcd. for [M−Cl]+ 1657.5619; found,
1657.5631.
1
IrLG2: (Yield: 40%). H NMR (δ (ppm), CDCl3, 400 MHz):
8.71 (s, 1H), 8.61 (s, 1H), 8.09 (d, J = 7.6 Hz, 16H), 7.77 (s,
2H), 7.72–7.70 (m, 12H), 7.59 (d, J = 5.2 Hz, 2H), 7.47 (d, J =
8.4 Hz, 18H), 7.38–7.30 (m, 18H), 7.27–7.23 (m, 17H), 7.05 (d,
J = 5.6 Hz, 1H), 6.95 (d, J = 5.6 Hz, 1H), 6.91 (d, J = 6.0 Hz,
1H), 6.86–6.77 (m, 3H), 6.75–6.69 (m, 8H), 6.18 (d, J = 7.2 Hz,
2H), 5.26 (s, 8H), 4.63–4.62 (m, 8H), 2.85 (t, J = 6.8 Hz, 2H),
Acknowledgements
The financial support of this work from National Science Foun-
dation of China (NSFC) under Project Nos. 20904038 and
21072218 is gratefully acknowledged.
2590 | Dalton Trans., 2012, 41, 2582–2591
This journal is © The Royal Society of Chemistry 2012