Eur. J. Inorg. Chem. 2007 © WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2007 ... · 2007. 1....
Transcript of Eur. J. Inorg. Chem. 2007 © WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2007 ... · 2007. 1....
Eur. J. Inorg. Chem. 2007 · © WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2007 · ISSN 1434–1948
SUPPORTING INFORMATION
Title: Blue-Light-Emitting Complexes: Cationic (2-Phenylpyridinato)iridium(III) Complexes with Strong-Field Ancillary Ligands Author(s): Chong Shik Chin,* Min-Sik Eum, Song yi Kim, Choongil Kim, Sung Kwon Kang Ref. No.: I200600920
Experimental details and spectroscopic data
1H-, 13C and 31P-NMR spectra were recorded on a Varian 200, 300 or 500 MHz
spectrometer. Nicolet 205 instrument was used to measure infrared spectra. Absorption spectra
measured on an Agilent 8453 UV-visible spectrophotometer. Steady state emission spectra were
measured on a JY Horiba Fluorolog-3 spectrofluorimeter. Phosphorescence lifetime measurements
were performed on a Tektronix model TDS 2022 oscilloscope with photomultiplier tube through a
monochromator by exciting the argon-charged sample at the third harmonic 355 nm of Q-switched
Nd:Yag laser with a pulse duration of 5 ns and a repetition rate of 10 Hz at room temperature.
Quantum efficiency was calculated with using fac-Ir(ppy)3 as the reference in toluene (ΦPL = 0.40[1]).
Elemental analysis was carried out using a Carlo Erba EA1180 at the Organic Chemistry Research
Center, Sogang University. Electrochemical measurements were carried out using a CHI 900 using
Glassy carbon working (3 mm dia) platinum wire counter (spiral), and Ag/Ag+ reference electrodes.
X-ray intensity data were obtained by using a Bruker SMART APEX-II CCD diffractometer
equipped with graphite monochromated Mo Kα radiation (λ = 0.71073 Å) at 295 K for 4a. Initial
unit cell parameters were obtained from SMART software.[2] Data integration, correction for
Lorentz and polarization effects, and final cell refinement were performed by SAINTPLUS.[3] An
empirical absorption correction based on the multiple measurement of equivalent reflections was
applied using the program SADABS.[4] Structures were obtained by a combination of the direct
methods and difference Fourier syntheses and refined by full matrix least-squares on F2, using the
SHELXTL.[5] All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were added in
calculated positions.
Schlenk type glass wares were used in most of experiments for synthesis and measurements
although most of metal complexes are stable enough to be handled in air at room temperature.
2-Phenylpyridine (ppyH), PPh3, PPh2Me, P(OPh)3, pyridine, MeCN, AgOTf, Pd(PPh3)4, 2-
bromopyridine, 2,4-difluorophenylyboronic acid and 2-bromo-4-methylpyridine were purchased
from Aldrich. F2ppyH and F2MeppyH were synthesized by Suzuki coupling reactions.[6] IrCl3·x
H2O and CO were obtained from Pressure Chemicals and Dong-A Gas Co. (Korea), respectively.
Iridium complexes, (ppy)2Ir(μ-Cl)2Ir(ppy)2,[7] (n-Bu)4N[Ir(ppy)2(CN)2],[8] Ir(ppy)2(Cl)(CO),[9]
Ir(ppy)2(Cl)(PPh3)[10] and Ir(ppy)2(Cl)(P(OPh)3)[10] were synthesized by the literature methods.
Synthesis of [Ir(ppy)2L2]OTf (2). Compounds 2b – 2e, 2F2 and 2F2Me have been prepared
practically by the same method described below for 2a. Either AgPF6 or AgOTf was used to
precipitate AgCl to remove Cl ligand. Ancillary ligands PPh2Me, P(OPh)3, MeCN and py were
added to the reaction mixture before the elimination of AgCl. The yields were 80 – 90 %.
Synthesis of [Ir(ppy)2(CO)2](PF6) (2a). A reaction mixture of (ppy)2Ir(μ-Cl)2Ir(ppy)2 (1, 107
mg, 0.1 mmol) and AgPF6 (51 mg, 0.2 mmol) in CHCl3 (10 mL) was stirred under CO (1 atm) at 25
oC for two hours before the white solid (AgCl) was removed by filtration. Addition of hexane (30
ml) to the resulting solution yielded beige micro-crystals which were isolated by filtration, washed
with hexane (3 x 10 mL) and dried under vacuum. The yield was 120 mg and 86 % based on 2a. 1H
NMR (300 MHz; acetone-d6): δ 9.47 (d, J = 5.4 Hz, 2H), 8.39–8.50 (m, 4H), 8.01 (d, J = 7.8 Hz,
2H), 7.72 (t, J = 5.7 Hz, 2H), 7.17 (t, J = 7.5 Hz, 2H), 7.06 (t, J = 7.5 Hz, 2H), 6.19 (d, J = 7.5 Hz,
2H). 13C NMR (75 MHz, acetone-d6): δ 167.75, 167.11, 156.43, 147.43, 145.26, 142.32, 132.49,
130.80, 127.11, 126.74, 122.91, IR (KBr, cm–1): 2126, 2084 (s, νC≡O), 2044 (s, νC13
≡O), 843 (s, PF6–).
Anal. Calcd for IrC24N2H16F6O2: C, 41.09; H, 2.30; N, 3.99. Found: C, 41.03; H, 2.32; N, 3.84.
[Ir(ppy)2(PPh2Me)2](OTf) (2b). 1H NMR (500 MHz; CDCl3): δ 8.58 (d, J = 6.0 Hz, 2H),
7.79 (t, J = 8.0 Hz, 2H), 7.69 (d, J = 7.5 Hz, 2H), 7.48 (d, J = 8.0 Hz, 2H), 7.33 (t, J = 7.5 Hz, 2H),
7.28–7.21 (m, 6H), 7.14 (t, J = 7.5 Hz, 4H), 7.08 (t, J = 8.0 Hz, 4H), 6.96 (qu, J = 7.0 Hz, 2H),
6.82–6.76 (m, 6H), 5.73 (d, J = 7.5 Hz, 2H), 1.63 (d, J = 6.0 Hz, 6H). 13C NMR (126 MHz, CDCl3):
δ 167.89, 155.02, 154.31, 143.44, 138.66, 133.36, 131.64, 131.37, 131.65, 131.00, 130.27, 128.66,
128.42, 125.09, 124.06, 123.91, 121.03, 14.29. 31P NMR (202 MHz, CDCl3): δ –21.67 (s). IR (KBr,
cm–1): 1269, 1152 and 1031 (s, OTf–). Anal. Calcd for IrC49N2H42F3O3SP2: C, 56.04; H, 4.03; N,
2.67. Found: C, 56.15; H, 4.07; N, 2.61.
[Ir(ppy)2(P(OPh)3)2](OTf) (2c). 1H NMR (500 MHz; CDCl3); δ 9.28 (d, J = 5.5 Hz, 2H),
7.97 (m, 4H), 7.62 (d, J = 7.5 Hz, 2H), 7.11–7.04 (m, 20H), 6.92 (t, J = 7.0 Hz, 2H), 6.66 (t, J = 7.0
Hz, 2H), 6.54 (d, J = 7.5 Hz, 12H), 5.78 (m, 2H). 13C NMR (126 MHz, CDCl3): δ 167.87, 157.33,
154.52, 153.83, 152.64, 151.32, 143.10, 139.80, 131.33, 130.82, 130.33, 129.96, 129.33, 125.42,
124.78, 124.34, 123.98, 122.51, 121.01, 120.93, 119.96, 119.88, 119.31, 115.80. 31P NMR (202
MHz, CDCl3): δ 73.12 (s). IR (KBr, cm–1): 1271, 1163 and 1031 (s, OTf–). Anal. Calcd for
IrC59N2H46F3O9SP2: C, 55.79; H, 3.65; N, 2.21. Found: C, 55.64; H, 3.68; N, 2.23.
[Ir(ppy)2(py)2](OTf) (2d). 1H NMR (300 MHz; CD2Cl2): δ 8.61 (d, J = 5.7 Hz, 2H), 8.53–
8.50 (m, 4H), 7.96–7.89 (m, 6H), 7.60–7.57 (m, 2H), 7.46–7.41 (m, 6H), 6.91–6.86 (m, 4H), 6.36–
6.32 (m, 4H). 13C NMR (75 MHz, acetone-d6): δ 168.62, 152.56, 149.84, 148.61, 144.69, 139.39,
139.18, 132.61, 130.89, 127.14, 124.94, 124.29, 123.08, 120.26. IR (KBr, cm–1): 1267, 1151 and
1031 (s, OTf–). Anal. Calcd for IrC33N4H26F3O3S: C, 49.06; H, 3.24; N, 6.94; S. Found: C, 48.93; H,
3.21; N, 6.73.
[Ir(ppy)2(NCMe)2](OTf) (2e). 1H NMR (500 MHz; CDCl3): δ 9.11 (d, J = 5.0 Hz, 2H), 7.88–
7.96(m, 4H), 7.57(d, J = 7.5 Hz, 2H), 7.45 (t, J = 6.5 Hz, 2H), 6.91 (t, J = 7.5 Hz, 2H), 6.77 (t, J =
7.0 Hz, 2H), 6.10 (d, J = 7.5 Hz, 2H), 2.38 (s, NCCH3, 6H). 13C 125.7 MHz (CDCl3): δ 167.35,
151.42, 144.28, 143.99, 138.59, 131.52, 130.08, 124.21, 123.72, 122.83, 119.42, 119.30 (s, CH3CN),
4.17 (s, CH3CN). IR (KBr, cm–1): 2310, 2280 (w, νN≡CR), 1270, 1165 and 1030 (s, OTf–). Anal.
Calcd for IrC27N4H22F3O3S: C, 44.32; H, 3.03; N, 7.66. Found: C, 44.15; H, 3.00; N, 7.32.
[Ir(F2ppy)2(CO)2](PF6) (2aF2). 1H NMR (300 MHz; acetone-d6): δ 9.58 (d, J = 4.5 Hz, 2H),
8.60–8.48 (m, 4H), 7.79 (t, J = 2.7 Hz, 2H), 6.98–6.90 (m, 2H), 5.71 (dd, J = 7.8, 1.8 Hz, 2H). IR
(KBr, cm–1): 2142, 2108 (s, νC≡O), 2051 (s, νC13
≡O), 841 (s, PF6–). Anal. Calcd for
IrC24N2H12F10O2P: C, 37.26; H, 1.56; N, 3.62. Found: C, 37.15; H, 1.53; N, 3.51.
[Ir(F2Meppy)2(CO)2](OTf) (2aF2Me). 1H NMR (300 MHz; acetone-d6): δ 9.36 (d, J = 3.6
Hz, 2H), 8.38 (s, 2H), 7.62 (s, 2H), 6.95–6.87 (m, 2H), 5.74 (dd, J = 8.0, 2.1 Hz, 2H), 2.76 (s, 6H).
IR (KBr, cm–1): 2141, 2105 (s, νC≡O), 2052 (s, νC13
≡O), 826 (s, PF6–). Anal. Calcd for
IrC26N2H16F10O2P: C, 38.96; H, 2.01; N, 3.49. Found: C, 39.16; H, 2.06; N, 3.40.
[Ir(F2ppy)2(PPh2Me)2](OTf) (2bF2). 1H NMR (500 MHz; CDCl3): δ 8.78 (d, J = 5.5 Hz, 2H),
7.97 (dd, J = 8.3, 3.0 Hz, 2H), 7.81 (t, J = 7.5 Hz, 2H), 7.31 (t, J = 7.0 Hz, 4H), 7.23 (t, J = 6.5 Hz,
2H), 7.16–7.08 (m, 12H), 6.91 (t, J = 8.5 Hz, 4H), 6.46 (m, 2H), 5.20 (dd, J = 5.3, 3.0 Hz, 2H), 1.86
(d, J = 6.5 Hz, 6H). 31P NMR (202 MHz, CDCl3): δ –26.54. IR (KBr, cm–1): 1257, 1164 and 1031
(s, OTf–). Anal. Calcd for IrC49N2H38F7O3SP2: C, 52.45; H, 3.41; N, 2.50. Found: C, 52.58; H, 3.45;
N, 2.43.
[Ir(F2Meppy)2(PPh2Me)2](OTf) (2bF2Me). 1H NMR (500 MHz; CDCl3): δ 8.56 (d, J = 6.5
Hz, 2H), 7.76 (s, 2H), 7.30–7.23 (m, 6H), 7.12 (t, J = 7.5 Hz, 8H), 7.06–7.00 (m, 6H), 6.92 (t, J =
7.0 Hz, 4H), 6.44 (t, J = 11.5 Hz, 2H), 5.22 (d, J = 7.0 Hz, 2H), 2.50 (s, 6H), 1.78 (d, J = 4.5 Hz,
6H). 31P NMR (202 MHz, CDCl3): δ –26.03. IR (KBr, cm–1): 1260, 1154 and 1031 (s, OTf–). Anal.
Calcd for IrC51N2H42F7O3SP2: C, 53.26; H, 3.68; N, 2.44. Found: C, 53.41; H, 3.63; N, 2.35.
Synthesis of [Ir(ppy)2 (CO)(L)]OTf (3). Compounds 3 have been prepared by practically the
same method described below for 3a. The yields were 80 – 90 %.
Synthesis of [Ir(ppy)2(CO)(NCMe)](OTf) (3a). A reaction mixture of Ir(ppy)2(Cl)(CO) (110
mg, 0.2 mmol) and AgOTf (51 mg, 0.2 mmol) in CHCl3 (10 mL) was stirred under nitrogen at 25
oC for two hours before the white solid (AgCl) was removed by filtration. A 2.0 mL of MeCN was
added into the filtrate solution and the resulting solution was stirred for two hours under N2 before
hexane (50 mL) was added to yield pale-yellow micro-crystals which were collected by filtration,
washed with hexane (3 x 10 mL) and dried under vacuum. The yield was 102 mg or 84 % based on
3a. 1H NMR (300 MHz; CD3CN): δ 9.14 (dt, J = 5.7, 1.2 Hz, 1H), 9.04 (dt, J = 6.0 1.2 Hz, 1H),
8.17–8.13 (m, 6H), 7.75 (ddd, J = 7.8, 4.1, 1.2 Hz, 2H), 7.55–7.43 (m, 3H), 7.07–6.99 (m, 3H),
6.93–6.83 (m, 3H), 6.20 (dd, J = 7.7, 1.2 Hz, 1H), 5.89 (dd, J = 7.5, 0.9 Hz, 1H), 2.27 (s, 3H). 13C
NMR (75 MHz, CD3CN): δ 171.56, 167,19, 166.64, 157.96, 155.49, 152.22, 145.68, 144.27, 141.05,
141.02, 126.21, 125.94, 125.76, 125.57, 125.29, 124.98, 121.78, 118.17, 1.87. IR (KBr, cm–1): 2290
(w, νN≡CR), 2044 (s, νC≡O), 1253, 1168 and 1030 (s, OTf–). Anal. Calcd for IrC26N3H19F3O4S: C,
43.45 H, 2.66; N, 5.85. Found: C, 43.26; H, 2.62; N, 5.68.
[Ir(ppy)2(CO)(py)](OTf) (3b). 1H NMR (300 MHz; acetone-d6): δ 9.58 (d, J = 5.4 Hz, 1H),
8.86 (s, 1H), 8.50–8.46 (m, 2H), 8.34–8.21 (m, 3H), 8.11 (m, 1H), 7.95 (d, J = 8.1 Hz, 1H), 7.89 (d,
J = 7.8 Hz, 1H) 7.64–7.55 (m, 5H), 7.15–7.03 (m, 3H), 6.94 (td, J = 7.5, 1.2 Hz, 1H), 6.40 (d, J =
7.5 Hz, 1H), 6.15 (d, J = 7.1 Hz, 1H). 13C NMR (75 MHz, acetone-d6): δ 155.48, 154.81, 151.53,
141.35, 141.38, 140.60, 131.45, 131.39, 131.62, 130.48, 128.43, 126.91, 126.40, 126.40, 126.21,
126.05, 125.44, 125.14, 122.21. IR (KBr, cm–1): 2046 (s, νC≡O), 1265, 1157 and 1031 (s, OTf–).
Anal. Calcd for IrC29N3H21F3O4S: C, 46.03; H, 2.80; N, 5.55. Found: C, 46.06; H, 2.83; N, 5.50.
[Ir(ppy)2(CO)(PPh3)](OTf) (3c). 1H NMR (200 MHz; CDCl3): δ 8.47 (dd, J = 8.9, 5.8 Hz,
1H), 8.16 (d, J = 4.0 Hz, 1H), 7.87 (t, J = 7.4 Hz, 1H), 7.77–7.60 (m, 2H), 7.50 (d, J = 8.2 Hz, 1H),
7.48–7.41 (m, 3H), 7.34–7.25 (m, 6H) 7.18–6.99 (m, 12H), 6.89 (m, 2H), 6.00 (dd, J = 7.5, 4.6 Hz,
1H), 5.67 (d, J = 7.8 Hz, 1H). IR (KBr, cm–1): 2048 (s, νC≡O), 1268, 1153 and 1031 (s, OTf–). Anal.
Calcd for IrC42N2H31F3O4SP: C, 53.67; H, 3.32; N, 2.98. Found: C, 53.75; H, 3.37; N, 2.92.
[Ir(ppy)2(CO)(P(OPh)3)](OTf) (3d). 1H NMR (200 MHz, CDCl3): δ 9.26 (d, J = 5.8 Hz,
1H), 8.64 (d, J = 5.8 Hz, 1H), 8.18–7.99 (m, 2H), 7.88 (d, J = 8.0 Hz, 1H), 7.59-7.49 (m, 4H), 7.41
(t, J = 6.6 Hz, 1H), 7.18–6.92 (m, 12H), 6.84 (t, J = 6.4 Hz, 2H), 6.45 (d, J = 7.4 Hz, 6H), 6.04 (m,
1H), 5.80 (m, 1H). IR (KBr, cm–1): 2069 (s, νC≡O), 1267, 1162 and 1031 (s, OTf–). Anal. Calcd for
IrC42N2H31F3O7SP: C, 51.06; H, 3.16; N, 2.84. Found: C, 51.19; H, 3.14; N, 2.71.
Synthesis of [Ir(ppy)2 (NCMe)(L)]OTf (4). Compounds 4 have been prepared by practically
the same method described above for 3a except that Ir(ppy)2(Cl)L (L = PPh3, PPh2Me, P(OPh)3)
was used in MeCN. The yields were 80 – 90 %.
Synthesis of [Ir(ppy)2(NCMe)(PPh3)](OTf) (4a). 1H NMR (200 MHz; CDCl3): δ 8.75 (d, J =
5.0 Hz, 1H), 8.58 (d, J = 5.2 Hz, 1H), 7.91 (d, J = 6.8 Hz, 1H), 7.80 (t, J = 8.8 Hz, 1H), 7.57–7.42
(m, 3H), 7.33–7.10 (m, 12H), 6.97–6.69 (m, 10H) 6.62 (t, J = 8.8 Hz, 1H), 5.83 (d, J = 7.6 Hz, 1H),
2.17 (s, 3H). 31P NMR (81 MHz, CDCl3): δ 0.45 (s). IR (KBr, cm–1): 2280 (w, νN≡CR), 1269, 1161
and 1031 (s, OTf–). Anal. Calcd for IrC43N2H34F3O3SP: C, 54.19; H, 3.60; N, 4.41. Found: C,
54.32; H, 3.56; N, 4.36.
[Ir(ppy)2(PPh2Me)(NCMe)](OTf) (4b). 1H NMR (200 MHz; CDCl3): δ 8.85 (d, J = 5.8 Hz,
1H), 8.57 (d, J = 5.4 Hz, 1H), 8.00 (d, J = 8.0 Hz, 1H), 7.90 (t, J = 7.0 Hz, 1H), 7.66–7.07 (m, 15H),
7.00–6.79 (m, 5H), 6.24 (d, J = 8.0 Hz, 1H), 5.97 (m, 1H), 2.38 (s, 3H), 1.77 (d, J = 8.0 Hz, 3H).
31P NMR (81 MHz, CDCl3): δ –19.48 (s). IR (KBr, cm–1): 2280 (w, νN≡CR), 1269, 1163 and 1031 (s,
OTf–). Anal. Calcd for IrC38N3H32F3O3SP: C, 51.23; H, 3.62; N, 4.72. Found: C, 51.13; H, 3.67; N,
4.74.
[Ir(ppy)2(P(OPh)3)(NCMe)](OTf) (4c). 1H NMR (200 MHz; CDCl3): δ 9.51 (d, J = 6.0 Hz,
1H), 9.13 (d, J = 5.7 Hz, 1H), 8.06–7.95 (m, 2H), 7.78 (t, J = 8.0 Hz, 1H), 7.67 (s, 1H), 7.63–7.55
(m, 3H), 7.46–7.34 (m, 3H), 7.20–7.12 (m, 4H), 7.07–6.70 (m, 13H), 6.28 (d, J = 7.6 Hz, 1H), 5.79
(t, J = 7.8 Hz, 1H), 2.07 (s, 3H). 31P NMR (81 MHz, CDCl3): δ 78.62 (s). IR (KBr, cm–1): 2286 (w,
νN≡CR), 1269, 1163 and 1031 (s, OTf–). Anal. Calcd for IrC43N3H34F3O6SP: C, 51.59; H, 3.42; N,
4.20. Found: C, 51.67; H, 3.45; N, 4.27.
[1] K. A. King, P. J. Spellane, R. J. Watts, J. Am. Chem. Soc. 1985, 107, 1431–1432.
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Inc.: Madison, WI 1998.
[3] SAINTPLUS, V 5.00 Software for the CCD Detector System; Bruker Analytical X-ray
Systems, Inc.: Madison, WI 1998.
[4] SADABS. Program for absorption correction using SMART CCD based on the method of:
R.H. Blessing, Acta Crystallogr. 1995, A51, 33.
[5] G. M. Sheldrick, SHELXTL, V 6.1; Bruker Analytical X-ray Systems, Inc.: Madison, WI 1997.
[6] O. Lohse, P. Thevenin, E. Waldvogel, Synlett 1999, 1, 45–48.
[7] M. Nonoyama, Bull. Chem. Soc. Jpn. 1974, 47, 767–768.
[8] M. K. Nazeeruddin, R. Humphrey-Baker, D. Berner, S. Rivier, L. Zuppiroli, M. Graetzel, J.
Am. Chem. Soc. 2003, 125, 8790–8797.
[9] W. J. Finkenzeller, P. Stößel, H. Yersin, Chem. Phys. Lett. 2004, 397, 289–295.
[10] C.-L. Lee, R. R. Das, J.-J. Kim, Curr. Appl. Phys. 2005, 5, 309–313.
1H NMR spectrum of [Ir(ppy)2(CO)2](PF6) (2a) at 300 MHz in acetone-d6
13C NMR spectrum of [Ir(ppy)2(CO)2](PF6) (2a) at 75 MHz in acetone-d6
1H NMR spectrum of [Ir(ppy)2(PPh2Me)2](OTf) (2b) at 500 MHz in CDCl3
13C NMR spectrum of [Ir(ppy)2(PPh2Me)2](OTf) (2b) at 126 MHz in CDCl3
1H NMR spectrum of [Ir(ppy)2(P(OPh)3)2](OTf) (2c) at 500 MHz in CDCl3
13C NMR spectrum of [Ir(ppy)2(P(OPh)3)2](OTf) (2c) at 126 MHz in CDCl3
1H NMR spectrum of [Ir(ppy)2(py)2](OTf) (2d) at 300 MHz in acetone-d6
13C NMR spectrum of [Ir(ppy)2(py)2](OTf) (2d) at 75 MHz in acetone-d6
1H NMR spectrum of [Ir(ppy)2(NCMe)2](OTf) (2e) at 500 MHz in CDCl3
13C NMR spectrum of [Ir(ppy)2(NCMe)2](OTf) (2e) at 126 MHz in CDCl3
1H NMR spectrum of [Ir(F2ppy)2(CO)2](OTf) (2aF2) at 300 MHz in acetone-d6
1H NMR spectrum of [Ir(F2Meppy)2(CO)2](OTf) (2aF2Me) at 300 MHz in acetone-d6
1H NMR spectrum of [Ir(F2ppy)2(PPh2Me)2](OTf) (2bF2) at 500 MHz in CDCl3
1H NMR spectrum of [Ir(F2Meppy)2(PPh2Me)2](OTf) (2bF2Me) at 500 MHz in CDCl3
1H NMR spectrum of [Ir(ppy)2(CO)(NCMe)](OTf) (3a) at 300 MHz in CD3CN
13C NMR spectrum of [Ir(ppy)2(CO)(NCMe)](OTf) (3a) at 75 MHz in CD3CN
1H NMR spectrum of [Ir(ppy)2(CO)(py)](OTf) (3b) at 300 MHz in acetone-d6
13C NMR spectrum of [Ir(ppy)2(CO)(py)](OTf) (3b) at 75 MHz in acetone-d6
1H NMR spectrum of [Ir(ppy)2(CO)(PPh3)](OTf) (3c) at 200 MHz in CDCl3
1H NMR spectrum of [Ir(ppy)2(CO)(P(OPh)3)](OTf) (3d) at 200 MHz in CDCl3
1H NMR spectrum of [Ir(ppy)2(NCMe)(PPh3)](OTf) (4a) at 200 MHz in CDCl3
1H NMR spectrum of [Ir(ppy)2(NCMe)(PPh2Me)](OTf) (4b) at 200 MHz in CDCl3
1H NMR spectrum of [Ir(ppy)2(NCMe)(P(OPh)3)](OTf) (4c) at 200 MHz in CDCl3
Table S1. Details of Crystallographic Data Collection for 4a
4a
Chemical formula C43H34F3IrN3O3PS
Chemical formula weight 952.96
Temp, K 295(2)
crystal dimension, mm 0.05 x 0.04 x 0.04
crystal system monoclinic
space group P2(1)/n
color of crystal Yellow
a, Å 10.5070(4)
b, Å 26.5922(9)
c, Å 15.1862(16)
α, deg. 90
β, deg. 95.458(2)
γ, deg. 90
V, Å3 4223.9(3)
Z 4
ρ(calc), gcm-1 1.499
μ, mm-1 3.302
F(000) 1888
Radiation Mo Kα
wavelength 0.71073
θ range, deg 1.53-27.50
hkl range -13 ≤ h ≤ 13
-34 ≤ k ≤ 34
-19 ≤ l ≤ 19
no. of reflns 81836
no. of unique data 9706
Completeness to theta = 27.50 100 %
No. of data/restraints/parameters 9706/1/449
Refinements method Full-matrix least-squares on F2
R1 0.0700
wR2 0.1654
GOF 1.084
R1 = [Σ⏐Fo⏐−⏐Fc⏐/⏐Fo⏐], wR2 = [Σw(Fo2 − Fc
2)2/Σw (Fo2) 2]0.5
w = 1/ [σ2(Fo2) + (0.0388P)2 + 1.8667P ] where P = (Fo2 + 2Fc2) / 3
PL decay measurement data
Cyclic voltamogram
Cyclicvoltamograms of [Ir(ppy)2(L)2]OTf (2) in MeCN. L = CO (-----), PPh2Me (…..), MeCN (⎯⎯).