Paper
NJC
1
3
C NMR (151 MHz, CDCl
3
) d 157.11, 148.97, 148.38, 138.99, 129.03, 28.83, 25.46, 22.52, 21.37, 14.04; HRMS MALDI-TOF (m/z) calcd
+
1
28.76, 127.03, 123.23, 121.75, 115.48, 21.30; HRMS MALDI-TOF for C36H36IrN O 751.2386; found 752.4604 [MH ].
3 3
(
m/z) calcd for C H N 169.0891; found 170.1395 [MH+].
IrG1. Bright yellow solids (0.12 g, 62%); m.p. 205–206 1C;
1
2
11
1
H NMR (600 MHz, CDCl ) d 8.64 (d, J = 5.7 Hz, 1H), 8.07 (s, 2H),
3
7
7
7
5
.64 (s, 1H), 7.59 (s, 1H), 7.55 (d, J = 7.2 Hz, 1H), 7.52 (d, J =
.3 Hz, 1H), 7.47 (dd, J = 8.4, 1.4 Hz, 2H), 7.38 (d, J = 4.4 Hz, 1H),
.31 (d, J = 5.8 Hz, 1H), 7.28 (d, J = 8.4 Hz, 3H), 7.12 (dd, J = 8.4,
.1 Hz, 1H), 6.91 (d, J = 4.6 Hz, 1H), 6.87 (t, J = 7.0 Hz, 1H), 6.81
Iridium complex (4)
Compound 2 (0.06 g, 0.35 mmol), IrCl ꢂ3H O (0.05 g, 0.14 mmol),
3
2
2-ethoxy ethanol (3 ml), and water (1 ml) were refluxed under an
argon atmosphere for 12 h. After cooling to room temperature,
the reaction was poured into water and stirred for 30 minutes.
The precipitate was collected by filtration, washed with water
and methanol, and dried to obtain a brick yellow chloro bridged
dimer 3. A mixture of dimer 3 (0.10 g, 0.08 mmol), 4-hydroxy
(t, J = 7.0 Hz, 1H), 6.79 (t, J = 6.9 Hz, 1H), 6.69 (d, J = 4.7 Hz, 2H),
6
2
2
1
1
1
1
3
.38 (d, J = 7.3 Hz, 1H), 6.14 (d, J = 7.2 Hz, 1H), 4.25 (t, J = 6.7 Hz,
H), 4.04–4.02 (m, 2H), 2.49 (s, 6H), 1.89–1.87 (m, 4H), 1.44 (m,
2H); C NMR (151 MHz, CDCl ) d 171.45, 168.50, 167.06,
59.00, 149.60, 149.24, 148.47, 148.44, 147.47, 144.23, 144.19,
41.40, 140.72, 140.62, 138.99, 132.63, 132.50, 129.64, 129.22,
28.24, 124.00, 123.74, 123.25, 123.21, 123.04, 122.62, 122.31,
21.19, 120.60, 119.58, 119.08, 116.19, 108.08, 69.63, 43.02,
4.65, 32.08, 29.07, 28.74, 27.07, 25.66, 21.35, 21.29; HRMS
1
3
3
2 3
picolinic acid (0.04 g, 0.27 mmol), Na CO (0.76 g, 0.72 mmol)
and 2-ethoxy ethanol (8 ml) was heated at 120 1C under a N2
atmosphere for 15 h. After cooling the mixture to room tem-
perature, a precipitate was filtered off and washed with water
and ether. The crude product was purified by column chromato-
4 3
MALDI-TOF (m/z) calcd for C56H59IrN O 1028.4216; found
graphy on silica gel eluting with a mixture of acetone:CH
2
Cl
give yellow solids (0.095 g, 80%); m.p. 4 350 1C; H NMR (600
MHz, CDCl ) d 13.88 (s, 1H), 8.52 (d, J = 5.9 Hz, 1H), 7.68 (s, 1H),
.63 (s, 1H), 7.58–7.54 (m, 2H), 7.34 (t, J = 7.2 Hz, 2H), 7.23 (d, J =
2
to
+
1027.7946 [M ].
1
IrG2. Bright yellow solids (0.15 g, 67%); m.p. 250–252 1C;
3
1
H NMR (600 MHz, CDCl ) d 8.64 (d, 1H), 8.15 (s, 6H), 7.67 (d,
3
7
4
7
J = 7.4 Hz, 2H), 7.59 (s, 4H), 7.55 (d, J = 6.8 Hz, 2H), 7.49 (d, J =
.9 Hz, 1H), 7.16–7.13 (m, 1H), 6.98 (d, J = 5.9 Hz, 1H), 6.90 (t, J =
.4 Hz, 1H), 6.84 (t, J = 7.4 Hz, 1H), 6.79–6.73 (m, 3H), 6.37
5.7 Hz, 1H), 7.44–7.40 (m, 6H), 7.34 (d, J = 7.7 Hz, 2H), 7.30 (d,
J = 8.2 Hz, 4H), 7.13 (dd, J = 8.4, 5.1 Hz, 1H), 6.87(d, J = 7.0 Hz,
1
3
(
(
1
1
1
d, J = 7.6 Hz, 1H), 6.20 (d, J = 7.6 Hz, 1H), 2.54 (s, 6H); C NMR
151 MHz, CDCl ) d 177.57, 168.54, 166.91, 160.56, 148.98,
48.83, 148.79, 148.19, 147.50, 146.09, 144.33, 144.05, 139.65,
35.01, 132.67, 132.53, 129.70, 129.47, 126.22, 124.02, 123.86,
23.42, 123.29, 121.62, 120.99, 119.75, 119.29, 21.38, 21.33;
2
7
H), 6.79 (t, J = 6.3Hz, 2H), 6.75(t, J = 5.9 Hz, 2H), 6.68(d, J =
.0 Hz, 2H) 6.37 (d, J = 6.1Hz, 1H), 6.13 (d, J = 6.0 Hz, 1H), 4.52
3
(t, J = 6.7 Hz, 2H), 4.11 (t, J = 6.0 Hz, 2H), 2.46 (s, 3H), 2.42 (s, 3H),
2
1
1
1
1
1
.13–2.04 (m, 2H), 2.02–1.93 (m, 2H), 1.78–1.68 (m, 2H), 1.67–
1
3
.61 (m, 2H), 1.46 (s, 36H); C NMR (151 MHz, CDCl ) d 171.56,
3
3 3
HRMS MALDI-TOF (m/z) calcd for C30H24IrN O 667.1447; found
68.49, 167.06, 159.03, 149.51, 149.09, 148.50, 148.43, 147.42,
44.22, 144.17, 142.41, 140.78, 140.56, 140.26, 140.01, 132.63,
32.49, 129.71, 129.67, 129.25, 128.35, 125.65, 124.02, 123.78,
23.54, 123.33, 123.23, 123.02, 122.14, 121.23, 120.65, 119.60,
+
6
67.4183 [M ].
Iridium complexes IrG0–IrG3
A mixture of compound 4 (0.10 g, 0.15 mmol), K
.16 mmol), and 18-crown-6 (2.00 mg, 0.01 mmol) in 1 : 2 THF– 29.02, 28.84, 27.03, 25.85, 21.33, 21.21; HRMS MALDI-TOF (m/z)
2
3
CO (0.02 g, 119.32, 119.10, 116.14, 110.19, 109.19, 69.68, 43.45, 34.73, 32.07,
0
+
DMF (15 ml) was degassed with N for 10 min and then stirred calcd for C H IrN O 1470.6625; found 1471.2269 [M ].
2
88 89
6 3
at 55 1C for 1 h. 1-Bromohexane, L1, L2, or L3 (0.25 mmol) was
then added, and the mixture was stirred for 24 h. Then a small
IrG3. Bright yellow solids (0.13 g, 62%); m.p. 290–292 1C;
H NMR (600 MHz, CDCl ) d 8.65 (d, J = 5.9 Hz, 1H), 8.45 (d, J =
1
3
amount of water and the solutions were extracted with ethyl 1.7 Hz, 2H), 8.26 (d, J = 1.5 Hz, 4H), 8.15 (d, J = 1.5 Hz, 8H), 7.88
acetate (50 ml ꢁ 2). The combined organic phase was washed (d, J = 8.7 Hz, 2H), 7.81 (d, J = 1.8 Hz, 1H), 7.80 (d, J = 1.9 Hz,
with water (50 ml) and brine solution (50 ml), dried by using 1H), 7.62 (s, 2H), 7.61 (s, 8H), 7.54 (d, J = 7.3 Hz, 1H), 7.48–7.40
Na
2 4
SO , filtered, and evaporated. The crude product was pur- (m, 10H), 7.37 (d, J = 8.1 Hz, 1H), 7.35–7.31 (m, 9H) 7.17 (dd, J =
ified by column chromatography eluting with acetone–CH Cl . 8.6, 5.1 Hz, 1H) 6.86 (t, J = 6.9 Hz, 2H), 6.74 (t, J = 7.4 Hz, 2H),
2
2
IrG0. Bright yellow solids (0.11 g, 67%); m.p. 333–335 1C; 6.69 (d, J = 4.7 Hz, 1H), 6.64 (t, J = 7.9 Hz, 1H), 6.37 (d, J = 7.5 Hz,
1
H NMR (600 MHz, CDCl ) d 8.66 (d, J = 5.7 Hz, 1H), 7.65 (s, 1H), 1H), 6.12 (d, J = 7.4 Hz, 1H), 4.65 (t, J = 7.1 Hz, 2H), 4.14 (t, J =
3
7.61 (s, 1H), 7.55 (d, J = 7.2 Hz, 1H), 7.53 (d, J = 7.4 Hz, 1H), 7.40 6.2 Hz, 2H), 2.45 (s, 3H), 2.40 (s, 3H), 2.17 (t, J = 7.6 Hz, 2H), 2.01
(
d, J = 4.3Hz, 1H), 7.36–7.32 (m, 2H), 7.16–7.13 (m, 1H), 6.95 (d, (dd, J = 14.4, 8.3 Hz, 2H), 1.88–1.78 (m, 2H), 1.76–1.66 (m, 2H),
1
3
J = 4.5 Hz, 1H), 6.87 (t, J = 7.1 Hz, 1H), 6.81 (t, J = 7.1, 1H), 6.76 1.45 (s, 72H); C NMR (151 MHz, CDCl
3
) d 171.59, 168.54,
(d, J = 6.9 Hz, 1H), 6.75–6.72 (m, 1H), 6.70 (t, J = 7.2 Hz, 1H), 167.10, 159.04, 149.40, 149.04, 148.51, 148.49, 148.40, 147.39,
6
2
2
.39 (d, J = 7.4 Hz, 1H), 6.15 (d, J = 7.3 Hz, 1H), 4.31–4.07 (m, 144.19, 144.08, 142.48, 141.49, 140.84, 140.68, 140.61, 140.22,
H), 2.52 (d, J = 5.6 Hz, 6H), 1.93 (s, 2H), 1.46 (d, J = 21.3 Hz, 132.62, 132.46, 130.58, 129.69, 129.28, 128.82, 128.36, 126.08,
1
3
H), 1.33 (d, J = 3.1 Hz, 4H), 0.89 (s, 3H); C NMR (151 MHz, 125.97, 124.03, 123.78, 123.66, 123.56, 123.53, 123.19, 123.07,
CDCl ) d 171.51, 168.50, 167.07, 159.11, 149.64, 149.28, 148.51, 123.01, 122.08, 121.28, 120.67, 119.94, 119.58, 119.31, 119.12,
3
1
1
1
48.44, 148.43, 147.50, 144.24, 144.20, 140.67, 140.60, 132.64, 116.18, 111.23, 110.90, 109.14, 69.73, 43.65, 34.73, 32.06, 29.72,
32.51, 129.64, 129.22, 128.26, 124.00, 123.74, 123.22, 123.06, 28.91, 27.09, 25.99, 21.34, 21.21; HRMS MALDI-TOF (m/z) calcd
+
22.36, 121.19, 120.60, 119.58, 119.09, 69.97, 31.57, 29.72, for C152
H
149IrN10
O
3
2356.1477; found 2356.8177 [M ].
This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2021
New J. Chem., 2021, 45, 7694–7704 | 7697