Inorganic Chemistry
Article
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give a white solid product (3.24 g, 88%). H NMR (400 MHz, CDCl ,
added to an dry CH Cl solution of colored Ir(III) μ-chloro-bridged
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2
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dimer (0.32 g, 0.24 mmol)/(0.55 g, 0.41 mmol)/(0.28 g, 0.21 mmol).
The reaction solution was magnetically stirred at room temperature for
6 h. The inorganic salt was removed by centrifugation, and the solvent
was evaporated to dryness under vacuum. The designed coumarin-
based Ir(III) complex isomers were isolated with silica gel preparative
thin-layer chromatography (TLC) using proper developing solvents.
Caution: Thallium(I) acetylacetonate (Tl(acac)) must be dealt with
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carefully because of its extreme toxicity.
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IrC5. Yield: 0.13 g, 36%. H NMR (400 MHz, CDCl , δ): 8.67 (dd, J
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= 5.6, 0.8 Hz, 2H), 8.53 (d, J = 10.0 Hz, 2H), 8.06 (d, J = 8.4 Hz, 2H),
7.88 (td, J = 8.0, 1.6 Hz, 2H), 7.28 (m, 2H), 6.72 (d, J = 8.4 Hz, 2H),
6.43 (d, J = 10.0 Hz, 2H), 6.23 (d, J = 8.4 Hz, 2H), 5.27 (s, 1H), 1.81
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(s, 6H). C NMR (100 MHz, CDCl , δ): 185.15, 167.13, 160.50,
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151.75, 149.14, 145.45, 140.48, 139.25, 137.46, 136.11, 122.80,
122.42, 117.37, 116.62, 115.93, 100.76, 28.68. FAB-MS (m/z): 736
+
[M] . Anal. Calcd for C H IrN O : C, 53.87; H, 3.15; N, 3.81.
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Found: C, 53.76; H, 3.10; N, 3.72%.
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IrC7. Yield: 0.11 g, 17%. H NMR (400 MHz, CDCl , δ): 8.55 (d, J
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= 5.2 Hz, 2H), 7.96 (d, J = 8.0 Hz, 2H), 7.90 (td, J = 7.6, 1.2 Hz, 2H),
7.55 (s, 2H), 7.31 (m, 2H), 7.30 (d, J = 9.6 Hz, 2H), 6.23 (s, 2H), 6.20
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(d, J = 9.6 Hz, 2H), 5.27 (s, 1H), 1.81 (s, 6H). C NMR (100 MHz,
CDCl , δ): 185.09, 166.70, 161.30, 150.65, 148.67, 148.53, 143.57,
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139.52, 137.63, 130.72, 123.28, 119.97, 119.78, 116.25, 111.55,
+
100.81, 28.74. FAB-MS (m/z): 736 [M] . Anal. Calcd for
C H IrN O : C, 53.87; H, 3.15; N, 3.81. Found: C, 53.79; H,
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.33 mmol)/(0.51 g, 0.44 mmol)/(0.46 g, 0.40 mmol) was
3.09; N, 3.71%.
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correspondingly added for the Stille cross-coupling reaction. The
reaction was allowed to proceed at 110 °C for 16 h. After the reaction
solution was recovered to room temperature, the solvent was
evaporated to dryness under reduced pressure. The target ligands
were isolated by silica gel column chromatography using CH Cl as
IrC7-A. Yield: 0.10 g, 15%. H NMR (400 MHz, CDCl , δ): 8.53 (d,
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J = 5.6 Hz, 1H), 8.51 (d, J = 6.0 Hz, 1H), 8.00 (d, J = 8.4 Hz, 1H), 7.91
(dd, J = 6.4, 1.6 Hz, 2H), 7.86 (td, J = 7.8, 1.6 Hz, 1H), 7.61 (d, J = 8.0
Hz, 1H), 7.54 (s, 1H), 7.39 (d, J = 9.6 Hz, 1H), 7.31−7.23 (m, 3H),
6.99 (d, J = 8.0 Hz, 1H), 6.16 (d, J = 9.6 Hz, 1H), 6.11 (s, 1H), 6.03 (d,
J = 9.6 Hz, 1H), 5.29 (s, 1H), 1.81 (s, 3H), 1.78 (s, 3H). C NMR
(100 MHz, CDCl , δ):185.08, 184.55, 167.74, 165.79, 161.52, 161.42,
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eluent.
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L-C5. Yield: 1.23 g, 83%. H NMR (400 MHz, CDCl , δ): 8.76 (dd,
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160.89, 150.95, 150.38, 149.66, 149.21, 148.42, 143.63, 143.30,
137.70, 137.34, 136.85, 133.54, 130.49, 123.10, 122.54, 121.56,
120.11, 119.74, 119.15, 119.02, 116.56, 115.61, 110.95, 100.78, 28.68.
+
FAB-MS (m/z): 736 [M] . Anal. Calcd for C H IrN O : C, 53.87;
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H, 3.15; N, 3.81. Found: C, 53.80; H, 3.10; N, 3.74%.
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IrC8. Yield: 0.12 g, 37%. H NMR (400 MHz, CDCl , δ): 9.12 (d, J
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Anal. Calcd for C H NO : C, 75.33; H, 4.06; N, 6.27. Found: C,
= 8.4 Hz, 2H), 8.53 (dd, J = 5.6 Hz, 2H), 7.94 (td, J = 8.0, 1.6 Hz, 2H),
7.54 (d, J = 9.6 Hz, 2H), 7.28 (m, 2H), 6.75 (d, J = 8.0 Hz, 2H), 6.23
(d, J = 1.6 Hz, 2H), 6.21 (s, 2H), 5.27 (s, 1H), 1.81 (s, 6H). C NMR
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5.22; H, 4.13; N, 6.16%.
L-C7. Yield: 1.65 g, 83%. H NMR (400 MHz, CDCl , δ): 8.74 (dd,
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J = 4.8, 0.8 Hz, 1H), 7.98 (dd, J = 8.0, 1.6 Hz, 1H), 7.95 (s, 1H), 7.81
(100 MHz, CDCl , δ): 185.17, 165.33, 160.88, 159.60, 151.79, 148.10,
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(
m, 2H), 7.75 (d, J = 9.2 Hz, 1H), 7.58 (d, J = 8.0 Hz, 1H), 7.31 (m,
145.38, 138.27, 132.20, 129.54, 127.97, 124.82, 122.32, 113.74,
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H), 6.46 (dd, J = 9.4, 1.4 Hz, 1H). C NMR (100 MHz, CDCl , δ):
111.34, 100.71, 28.67. FAB-MS (m/z): 736 [M] . Anal. Calcd for
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60.80, 155.28, 154.46, 150.00, 142.99, 142.94, 137.04, 128.14,
C H IrN O : C, 53.87; H, 3.15; N, 3.81. Found: C, 53.77; H, 3.16;
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23.19, 122.96, 120.92, 119.10, 116.94, 115.00. FAB-MS (m/z): 223
N, 3.75%.
+
[
M] . Anal. Calcd for C H NO : C, 75.33; H, 4.06; N, 6.27. Found:
X-ray Crystallography. High-quality single crystals of IrC5, IrC7,
and IrC7-A for X-ray diffraction investigation were obtained by slowly
diffusing methanol into their chloroform solutions. The selected single
crystals were measured with a Φ and ω scan modes on a Bruker
SMART CCD diffractometer (Mo Kα radiation and λ = 0.71073 Å).
Direct methods and difference Fourier syntheses were applied to solve
the molecular structures. Structural refinements were achieved by full-
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C, 75.19; H, 4.09; N, 6.18%.
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L-C8. Yield: 1.45 g, 81%. H NMR (400 MHz, CDCl , δ): 8.75 (dd,
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J = 4.8, 0.8 Hz, 1H), 8.11 (dd, J = 8.0, 1.6 Hz, 1H), 8.03 (d, J = 8.0 Hz,
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=
H), 7.83 (td, J = 7.8, 1.6 Hz, 1H), 7.79 (d, J = 9.6 Hz, 1H), 7.54 (dd, J
7.6, 1.6 Hz, 1H), 7.41 (t, J = 7.6 Hz, 1H), 7.31 (ddd, J = 7.6, 4.8, 0.8
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Hz, 1H), 6.47 (d, J = 9.6 Hz, 1H). C NMR (100 MHz, CDCl , δ):
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60.27, 157.04, 153.06, 151.24, 149.81, 143.97, 136.45, 133.66,
matrix least-squares techniques against F in SHELXL-97 program. A
28.57, 125.39, 124.56, 122.78, 119.21, 116.43. FAB-MS (m/z): 223
riding model was used to calculate and refine the positions of hydrogen
isotropically. Likewise, all other non-hydrogen atoms were also refined
+
[
M] . Anal. Calcd for C H NO : C, 75.33; H, 4.06; N, 6.27. Found:
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C, 75.22; H, 4.11; N, 6.19%.
isotropically. SADABS was applied for absorption corrections.
General Synthetic Procedure for IrC5/IrC7/IrC7-A/IrC8. To a
Computational Details. DFT calculations for all of the obtained
ppy-type coumarin-based cyclometalated Ir(III) complex isomers were
conducted using the B3LYP. C, H, O, and N atoms adopted the 6-31G
(d, p) basis set for calculations, while a LanL2DZ basis set was
solvent mixture of 2-ethoxyethanol and H O (3/1, v/v) in a nitrogen
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atmosphere were added L-C5 (0.25 g, 1.12 mmol)/L-C7(0.44 g, 1.97
mmol)/L-C8(0.21 g, 0.94 mmol) and IrCl ·nH O (60 wt % Ir
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content) (0.16 g, 0.51 mmol)/(0.29 g, 0.90 mmol)/(0.14 g, 0.43
mmol). The reaction mixture was magnetically stirred at 110 °C for 16
h. Once the resultant mixture was cooled to room temperature, we
poured it into a saturated solution of NaCl. The precipitated colored
Ir(III) μ-chloro-bridged dimer was filtrated out and dried in vacuum.
Afterward, thallium(I) acetylacetonate [Tl(acac)] (0.16 g, 0.53
mmol)/(0.27 g, 0.90 mmol)/(0.14 g, 0.46 mmol) was correspondingly
employed for effective core potentials of Ir atoms.
TD-DFT
calculations were conducted to obtain the excitation behaviors based
on the optimized ground state (S ) geometries. In addition, the
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geometries of the lowest triplet excited state (T ) were optimized with
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the UB3LYP method and analyses of the natural transition orbital
(NTO) was conducted for S → T excitation. All the theoretical
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calculations were performed in the Gaussian 09 program.
C
Inorg. Chem. XXXX, XXX, XXX−XXX