European Journal of Inorganic Chemistry
10.1002/ejic.201900077
FULL PAPER
further purification. Chloro-bridged dimer Ir-Cl-1 (0.092 g, 0.05 mmol) and
The combined organic phase was dried and concentrated in vacuum,
and target product was purified by column chromatography on silica gel
2,2'-bipyridine (0.015 g, 0.1 mmol) were dissolved in methaol (5 ml) and
CH Cl (5 ml). The mixture was refluxed under argon, After 4 h, the
2
2
with CH
2
1
Cl
2
/ petroleum ether 1:1 (v/v) to afford white solid. 576 mg
solution was cooled to room temperature, and then a 10-fold excess of
potassium hexafluoro-phosphate was added. The suspension was stirred
for 2 h, and then filtered to remove insoluble inorganic salts. The
resulting solution was evaporated to dryness under reduced pressure.
(85 %). H NMR (400 MHz, CDCl ) δ 8.64 (ddd, J = 4.8, 1.7, 0.9 Hz, 1H),
7.71 (m, 1H), 7.61 (dt, J = 8.0, 1.0 Hz, 1H), 7.40 (d, J = 2.2 Hz, 2H), 7.35
(m, 4H), 7.22 (ddd, J = 7.4, 4.8, 1.1 Hz, 1H), 7.10 (m, 6H), 6.74 (dd, J =
3.0, 1.4 Hz, 1H). C NMR(101 MHz, CDCl
149.67, 142.38, 136.86, 129.89, 129.52, 123.66, 122.68, 120.77, 119.15,
115.52, 112.14, 109.99. C23 calcd: C, 81.40; N, 4.13; H, 5.05.
Found: C, 81.32; N, 4.10; H, 5.09. EI-MS (m/z): 340(M , 20 %).
3
13
3
): 158.98, 156.80, 156.24,
The residue was chromatographed on silica gel with elution by
1
2
CH Cl
2
/acetone 10: 1 (v/v) to afford a red solid. 73 mg (70 %). H NMR
H17NO
2
+
(400 MHz, DMSO) δ 8.84 (d, J = 8.2 Hz, 2H), 8.28 (m, 4H), 8.15 (d, J =
5
=
.0 Hz, 2H), 7.90 (t, J = 7.8 Hz, 2H), 7.73 (m, 2H), 7.57 (s, 2H), 7.45 (d, J
Ir-O: L-3 (0.082 g, 0.243 mmol) and IrCl (0.035 g, 0.1 mmol) were
charged to a 100 mL double-neck reaction bottle, followed by mixture of
-ethoxyethanol (9 mL) and H O (3 mL). The mixture was heated to 110
ºC for 24 h under N . H O (100 mL) was added and the resulting
precipitate was filtered. The product has been washed three times with
water and dried to give chloro-bridged dimer complex Ir-Cl-3 without
further purification. Chloro-bridged dimer Ir-Cl-3 (0.090 g, 0.05 mmol) and
3
5.6 Hz, 2H), 7.24 (m, 2H), 7.17 (d, J = 8.0 Hz, 2H), 6.99 (m, 8H), 6.84 (t,
13
J = 7.7 Hz, 2H), 6.69 (t, J = 7.7 Hz, 2H), 5.41 (d, J = 7.9 Hz, 2H).
NMR (101 MHz, DMSO) 166.34, 155.18, 149.98, 149.81, 148.82, 146.59,
C
2
2
2
2
1
1
1
7
46.54, 141.37, 141.19, 140.24, 138.18, 129.65, 129.34, 128.32, 128.07,
26.02, 125.13, 123.98, 123.80, 123.47, 122.76, 121.91, 119.99, 117.13,
16.33, 115.26, 114.36, 108.88. C56
.05; H, 2.87. Found: C, 56.34; N, 7.01; H, 2.91. ESI-MS
34 6 6 4
H F IrN O P calcd: C, 56.42; N,
2,2'-bipyridine (0.015 g, 0.1 mmol) were dissolved in methaol (5 ml) and
+
(
m/z):1047.50(M-PF
Synthesis and characterization of complex Ir-N
L-2: 2-Bromopyridine (0.158 g, mmol), (4-(diphenylamino)phenyl)
6
) .
CH Cl (5 ml). The mixture was refluxed under argon, After 4 h, the
2
2
solution was cooled to room temperature, and then a 10-fold excess of
potassium hexafluoro-phosphate was added. The suspension was stirred
for 2 h, and then filtered to remove insoluble inorganic salts. The
resulting solution was evaporated to dryness under reduced pressure.
1
boronic acid (0.347 g, 1.2 mmol), Pd[P(Ph) (0.012 g, 0.01 mmol) and
CO (0.553 g, 0.2 mmol) were charged to a 100 mL schlenck tube,
followed by H O (2 mL) and 1,4-Dioxane (4 mL). The mixture was heated
to 100 °C for 24 h under N . The resulting solution was saturated with
water and extracted with CH Cl three times. The combined organic
phase was dried and concentrated in vacuum, and target product was
purified by column chromatography on silica gel with CH Cl / petroleum
ether 1: 3 (v/v) to afford white solid, 260 mg (80 %). H NMR (CDCl ): δ
.66 (m, 1H), 7.88 (m, 2H), 7.70 (m, 2H), 7.28 (tt, 4H), 7.17 (m, 7H), 7.06
3 4
]
K
2
3
The residue was chromatographed on silica gel with elution by
2
1
2
CH Cl
2
/acetone 15: 1 (v/v) to afford a yellow solid. 74 mg (72 %).
H
2
NMR (400 MHz, DMSO) δ 8.87 (m, 2H), 8.30 (m, 2H), 8.17 (m, 2H), 7.77
m, 4H), 7.53 (m, 2H), 7.37 (m, 8H), 7.03 (m, 10H), 6.81 (m, 4H), 6.11 (m,
2
2
(
13
6
1
1
1
5
H). C NMR (101 MHz, DMSO) 165.90, 162.28, 157.66, 157.36, 155.28,
52.99, 149.81, 148.66, 148.48, 140.12, 137.75, 130.20, 129.86, 129.14,
28.87, 125.16, 123.09, 122.78, 121.65, 120.16, 117.41, 116.63, 112.61,
2
2
1
3
8
12.50. C56
40 6 4 4
H F IrN O P calcd: C, 57.48; N, 4.79; H, 3.45. Found: C,
13
(
1
m, 2H). C NMR (CDCl
32.97, 129.33, 127.77, 124.77, 123.27, 123.20, 121.46, 119.20.
calcd: C, 85.68; N, 8.69; H, 5.63. Found: C, 85.60; N, 8.63; H,
3
): 157.03, 149.48, 148.78, 147.49, 136.75,
+
7.41; N, 4.76; H, 3.49. ESI-MS (m/z): 1025.50 (M-PF
6
) .
23 18 2
C H N
+
Acknowledgements
5
.69. EI-MS (m/z): 323.25(M , 100 %).
Ir-N: L-2 (0.078 g, 0.243 mmol) and IrCl
charged to a 100 mL double-neck reaction bottle, followed by mixture of
-ethoxyethanol (9 mL) and H O (3 mL). The mixture was heated to 110
ºC for 24 h under N . H O (100 mL) was added and the resulting
This work was supported by National Natural Science
Foundation of China (21601069, 51672114), Natural Science
Foundation of Jiangsu Province of China (BK20160552,
BK20161357), Natural Science Foundation of the Higher
Education Institutions of Jiangsu Province (16KJB150011),
China Postdoctoral Science Foundation (2017M611746) and
Jiangsu Planned Projects for Postdoctoral Research Funds
3
(0.035 g, 0.1 mmol) were
2
2
2
2
precipitate was filtered. The product has been washed three times with
water and dried to give chloro-bridged dimer complex Ir-Cl-2 without
further purification. Chloro-bridged dimer Ir-Cl-2 (0.087 g, 0.05 mmol) and
2,2'-bipyridine (0.015 g, 0.1 mmol) were dissolved in methaol (5 ml) and
(
1701115B).
CH Cl (5 ml). The mixture was refluxed under argon, After 4 h, the
2
2
solution was cooled to room temperature, and then a 10-fold excess of
potassium hexafluoro-phosphate was added. The suspension was stirred
for 2 h, and then filtered to remove insoluble inorganic salts. The
resulting solution was evaporated to dryness under reduced pressure.
Keywords: N-embedded ligands
•
polycyclic ligands
•
phosphorescent cationic • iridium complexes • polystyrene films
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Chem. Int. Ed. 2017, 56, 5087.
The residue was chromatographed on silica gel with elution by
1
2
CH Cl
2
/acetone 10: 1 (v/v) to afford a red solid. 83 mg (84 %). H NMR
[2] Y. –K. Wang, Q. Sun, S. –F. Wu, Y. Yuan, Q. Li, Z. –Q. Jiang, M. –K.
Fung, L. –S. Liao, Adv. Funct. Mater. 2016, 26, 7929.
(
400 MHz, CDCl
3
) δ 8.62 (d, J = 8.0 Hz, 2H), 8.14 (m, 4H), 7.42 (m, 9H),
.19 (m, 12H), 7.00 (m, 13H), 6.70 (d, J = 7.6 Hz, 2H), 6.56 (t, J = 6.3 Hz,
7
2
1
1
[3] X. –Y. Wang, F. –D. Zhuang, R. –B. Wang, X. –C. Wang, X. –Y. Cao, J. –
Y. Wang, J. Pei, J. Am. Chem. Soc. 2014, 136, 3764.
13
H), 5.77 (s, 2H). C NMR (101 MHz, CDCl
50.38, 149.42, 147.88, 146.89, 139.63, 137.16, 136.28, 129.14, 127.97,
6
25.70, 125.13, 123.60, 123.14, 121.55, 118.61, 114.83. C56 IrN P
3
): 166.96, 155.75, 151.37,
[4] Y. –K. Wang, S. –H. Li, S. –F. Wu, C. –C. Huang, S. Kumar, Z. –Q. Jiang,
M. –K. Fung, L. –S. Liao, Adv. Funct. Mater. 2018, 28, 1706228.
[5] X. Zheng, X. Wang, Y. Qiu, Y. Li, C. Zhou, Y. Sui, Y. Li, J. Ma, X. Wang, J.
Am. Chem. Soc. 2013, 135, 14912.
H F
42 6
calcd: C, 59.20; N, 7.40; H, 3.73. Found: C, 59.12; N, 7.35; H, 3.77. ESI-
+
6
MS (m/z): 991.58(M-PF ) .
[
6] S. Suzuki, A. Nagata, M. Kuratsu, M. Kozaki, R. Tanaka, D. Shiomi, K.
Sugisaki, K. Toyota, K. Sato, T. Takui, K. Okada, Angew. Chem. Int. Ed.
2012, 51, 3193.
Synthesis and characterization of complex Ir-O
2 3
L-3: 2-(3,5-difluorophenyl)pyridine (0.382 g, 2 mmol), K CO (1.104 g, 8
mmol) and phenol (0.752 g, 8 mmol) were charged to a 100 mL double-
neck reaction bottle, followed by N-Methyl pyrrolidone (10 mL). The
[7] D. Sakamaki, D. Kumano, E. Yashima, S. Seki, Angew. Chem. Int. Ed.
2015, 54, 1.
mixture was heated to 190 ºC for 24 h under N
2
. The resulting solution
[8] M. Kuratsu, M. Kozaki, K. Okada, Angew. Chem. Int. Ed. 2005, 44, 4056.
was saturated with water and extracted with ethyl acetate three times.
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