Eur. J. Inorg. Chem. 2006 · © WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2006 · ISSN 1434–1948

SUPPORTING INFORMATION

Title: New Type of Photoluminescent Iridium Complex: Novel Synthetic Route for Cationic trans-Bis(2-phenylpyridinato)iridium(III) Complex Author(s): Chong Shik Chin,* Min-Sik Eum, Song yi Kim, Choongil Kim, Sung Kwon Kang Ref. No.: I200600888

Experimental details and spectroscopic data

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.

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 model 8453 UV-visible spectrophotometer. The steady state emission spectra were

measured on a JY Horiba model SPEX Fluorolog-3 spectrofluorimeter. Phosphorescence lifetime

measurements were performed on a Tektronix model TDS 2022 oscilloscope using 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 the room

temperature. Quantum efficiencies were calculated using fac-Ir(ppy)3 as the reference in toluene

(ΦPL = 0.40[1]). GC-mass spectra were obtained on a Hewlett-Packard HP5890a and VG-trio 2000

instruments. Elemental analysis and ESI TOF-mass were carried out with a Carlo Erba EA1180 and

a Waters LCT/KC433 at the Organic Chemistry Research Center, Sogang University.

X-ray intensity data were measured by using a Bruker SMART APEX-II CCD

diffractometer equipped with graphite monochromated Mo Kα radiation (λ = 0.71073 Å) at 233 K

and 173 K for 1 and 2, respectively. 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.

2-Phenylpyridine (ppyH), PPh3, P(OPh)3, 4-ethynyltoluene, MeCN, AgOTf, Pd(PPh3)4, 2-

bromopyridine, 2,4-difluorophenylyboronic acid, 2-bromo-5-methylpyridine and 2,4-

difluorophenylyboronic acid were purchased from Aldrich. F2ppyH and F2MeppyH were

synthesized by Suzuki coupling reactions using Pd(PPh3)4, 2-bromopyridine with 2,4-

difluorophenylyboronic acid and 2-bromo-5-methylpyridine with 2,4-difluoro- phenyl boronic

acid.[6] IrCl3·x H2O was obtained from Pressure Chemicals.

Iridium complexes, [Ir(H)2(NCMe)2(PPh3)2]+,[7] (ppy)2Ir(μ-Cl)2Ir(ppy)2,[8] and

Ir(ppy)2(Cl)(PPh3)[9] were synthesized by the literature methods.

Synthesis of [trans-Ir(ppy)2(PPh3)2]OTf (1), [trans-Ir(F2ppy)2(PPh3)2]OTf (1F2) and [trans-

Ir(F2Meppy)2(PPh3)2]OTf (1F2Me). These complexes have been prepared by the same method

described below for 1. The yields were 70 – 80 %.

Synthesis of [trans-Ir(ppy)2(PPh3)2](OTf) (1). A reaction mixture of [Ir(ppy)(NCMe)(-

CH=CH-(p-C6H4CH3))(PPh3)2](OTf) (5, 0.10 g, 0.09 mmol) and 2-phenylpyridine (ppyH, 0.04 g,

0.27 mmol) in 2-ethoxyethanol (10 mL) was refluxed for 5 h and cooled down to 25 oC before n-

pentane (30 mL) was added to precipitate pale yellow micro-crystals of 1 which were collected by

filtration, washed with n-pentane (3 x 10 mL), re-crystallized in CHCl3/n-pentane, and dried under

vacuum. The yield was 0.07 g and 70 % based on complex 1. 1H NMR (CDCl3, 500 MHz): δ 9.02

(m, 2H), 7.43-7.36 (m, 6H), 7.27-7.24 (m, 4H), 7.16 (t, J = 7.5 Hz, 6H), 7.07-7.05 (m, 2H), 6.97 (t,

J = 7.0 Hz, 2H), 6.91 (t, J = 8.0 Hz, 2H), 6.28-6.24 (m, 12H). 31P NMR (CDCl3, 202 MHz): δ −8.99

(s, PPh3). 13C NMR (CDCl3, 125.7 MHz): δ 166.11, 151.46, 148.93, 143.53, 138.92, 137.85, 133.70,

130.17, 129.17, 127.99, 125.68, 124.19, 123.95, 123.69, 119.69. HETCOR (1H (500 MHz) 13C

(125.7 MHz)): δ 9.02 151.46; 7.43-7.36 137.85, 124.19, 123.95, 123.69; 7.16 130.17; 7.07-

7.05 119.69; 6.97 129.17; 6.91 127.99; 6.28-6.24 133.70. Anal. Calcd for

IrC59H46F3N2O3P2S: C, 60.35; H, 3.95; N, 2.39. Found: C, 60.12; H, 3.99; N, 2.43. TOF mass: 1026,

Ir(ppy)2(PPh3)2; 764, Ir(ppy)2(PPh3). IR (KBr, cm-1): 1264, 1154 and 1031 (s, OTf−).

[trans-Ir(F2ppy)2(PPh3)2](OTf) (1F2). 1H NMR (CDCl3, 300 MHz): δ 8.98 (d, J = 4.8 Hz, 2H),

7.46-7.40 (m, 6H), 7.21 (t, J = 7.4 Hz, 6H), 6.97 (t, J = 7.8 Hz, 12H), 6.74 (m, 2H), 6.56 (d, J = 8.4

Hz, 2H), 6.32-6.26 (m, 12H). 13C NMR (CDCl3, 75.5 MHz): δ 162.63, 152.07, 149.65, 138.63,

133.36, 132.85, 130.66, 128.27, 124.62, 123.15, 122.87, 120.69, 120.48, 99.95, 99.59. 31P NMR

(CDCl3, 81 MHz): δ −7.92 (s, PPh3). Anal. Calcd for IrC59N2H42F7O3SP2: C, 56.86; H, 3.40; N, 2.25.

Found: C, 56.73; H, 3.43; N, 2.28. TOF mass: 1097, Ir(F2ppy)2(PPh3)2; 835, Ir(F2ppy)2(PPh3). IR

(KBr, cm-1): 1259, 1154 and 1030 (s, OTf−).

[trans-Ir(F2Meppy)2(PPh3)2](OTf) (1F2Me). 1H NMR (CDCl3, 300 MHz): δ 8.75 (d, J = 6.0

Hz, 2H), 7.28-7.19 (m, 10H), 6.98 (t, J = 7.4 Hz, 12H), 6.72 (m, 2H), 6.57 (d, J = 9.9 Hz, 2H), 6.34-

6.28 (m, 12H), 2.32 (s, 6H, F2Meppy). 13C NMR (CDCl3, 75.5 MHz): δ 162.47, 160.95, 159.21,

151.26, 150.22, 133.87, 133.16, 130.80, 128.54, 125.65, 125.42, 124.32, 123.84, 120.93, 100.20,

21.55. 31P NMR (CDCl3, 81 MHz): δ −8.48 (s, PPh3). Anal. Calcd for IrC61N2H46F7O3SP2: C, 57.50;

H, 3.64; N, 2.20. Found: C, 57.73; H, 3.69; N, 2.18. TOF mass: 1125, Ir(F2Meppy)2(PPh3)2; 863,

Ir(F2Meppy)2 (PPh3). IR (KBr, cm-1): 1265, 1156 and 1032 (s, OTf−).

Synthesis of [cis-Ir(ppy)2(PPh3)(P(OPh)3)]OTf (2), [cis-Ir(F2ppy)2(PPh3)(P(OPh)3)] OTf (2F2)

and [cis-Ir(F2Meppy)2(PPh3)(P(OPh)3)]OTf (2F2Me). These complexes have been prepared by the

same method described below for 2. The yields were 90 – 95 %.

Synthesis of [cis-Ir(ppy)2(PPh3)(P(OPh)3)](OTf) (2). A reaction mixture of cis-

Ir(ppy)2(Cl)(PPh3) (0.10 g, 0.13 mmol) and AgOTf (0.04 g, 0.15 mmol) in CHCl3 (10 mL) was

stirred under nitrogen at 25 oC for 1 h before the white solid (AgCl) was removed by filtration.

P(OPh)3 (0.05 g, 0.15 mmol) was added into the filtrate solution and the reaction mixture was

stirred under nitrogen at 25 oC for 1h before n-pentane (30 mL) was added to precipitate pale

yellow micro-crystals of 2 which were collected by filtration, washed with n-pentane (3 x 10 mL),

re-crystallized in CHCl3/n-pentane, and dried under vacuum. The yield was 0.15 g and 93 % based

on 2. 1H NMR (500 MHz; CDCl3); δ 8.93 (d, J = 5.5 Hz, 1H), 8.87 (d, J = 6.0 Hz, 1H), 7.95 (t, J =

7.5 Hz, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.80 (t, J = 8.0 Hz, 1H), 7.60 (dd, J = 7.8, 2.0 Hz, 1H), 7.48

(d, J = 8.0 Hz, 1H), 7.36 (t, J = 7.5 Hz, 3H), 7.31 (d, J = 7.5 Hz, 1H), 7.21 (td, J = 8.0, 1.5 Hz, 6H),

7.14 (t, J = 8.0 Hz, 6H), 7.09 (m, 1H), 7.04-6.94 (m, 12H), 6.86 (t, J = 7.5 Hz, 1H), 6.71-6.64 (m,

2H), 6.51 (d, J = 7.5 Hz, 6H), 6.03 (m, 1H), 5.18 (t, J = 8.0 Hz, 1H). 13C NMR (125.7 MHz,

CDCl3); δ 168.75, 167.65, 158.90, 157.71, 154.70, 153.75, 151.96, 151.83, 150.41, 149.76, 143.48,

143.10, 139.55, 139.00, 134.27, 132.12, 131.79, 131.16, 130.87, 130.53, 129.99, 129.94, 129.61,

128.58, 125.29, 125.01, 124.61, 124.39, 124.23, 124.06, 123.79, 121.15, 120.61, 119.72. HETCOR

(1H (500 MHz) 13C (125.7 MHz)): δ 8.93 153.75; 8.87 151.96; 7.95 139.00; 7.83 120.61;

7.80 130.87; 7.60 124.61; 7.48 121.15; 7.36 130.88; 7.31 125.01; 7.21 128.58;

7.14 134.27; 7.09 123.79; 6.96 125.29; 6.69 131.16; 6.66 132.12; 6.51 119.72;

6.03 132.12; 5.18 130.86. 31P NMR (CDCl3, 202 MHz): δ 71.13 (d, J = 22.6 Hz, P(OPh)3),

−1.73 (d, J = 22.6 Hz, PPh3). Anal. Calcd for IrC59N2H46F3O6SP2: C, 57.98; H, 3.79; N, 2.29.

Found: C, 57.86; H, 3.81; N, 2.30. TOF mass: 1074, Ir(ppy)2(PPh3)(P(OPh)3); 812,

Ir(ppy)2(P(OPh)3); 764, Ir(ppy)2(PPh3). IR (KBr, cm-1): 1270, 1161 and 1031 (s, OTf−).

[cis-Ir(F2ppy)2(PPh3)(P(OPh)3)](OTf) (2F2). 1H NMR (300 MHz; CDCl3); δ 8.89 (d, J = 6.0

Hz, 1H), 8.69 (d, J = 5.7 Hz, 1H), 8.11 (dd, J = 8.1, 3.0 Hz, 1H), 7.86 (t, J = 8.4 Hz, 1H), 7.71-7.69

(m, 2H), 7.31-7.19 (m, 5H), 7.12-7.08 (m, 6H), 7.06-6.98 (m, 6H), 6.89-6.79 (m, 9H), 6.41 (d, J =

7.5 Hz, 6H), 6.33 (m, 1H), 6.20 (m, 1H), 5.25 (m, 1H), 4.44 (t, J = 8.4 Hz, 1H). 31P NMR (CDCl3,

81 MHz): δ 68.52 (q, J = 11.8 Hz, P(OPh)3), −1.48 (s, PPh3). Anal. Calcd for IrC59N2H42F7O6SP2:

C, 54.75; H, 3.27; N, 2.16. Found: C, 54.55; H, 3.29; N, 2.21. TOF mass: 1146,

Ir(F2ppy)2(PPh3)(P(OPh)3); 884, Ir(F2ppy)2(P(OPh)3); 836, Ir(F2ppy)2(PPh3). IR (KBr, cm-1): 1272,

1163 and 1031 (s, OTf−).

[cis-Ir(F2Meppy)2(PPh3)(P(OPh)3)](OTf) (2F2Me). 1H NMR (300 MHz; CDCl3); δ 8.73 (d, J

= 6.0 Hz, 1H), 8.63 (d, J = 6.6 Hz, 1H), 7.95 (s, 1H), 7.44 (s, 1H), 7.35-7.31 (m, 5H), 7.20-7.16 (m,

6H), 7.09-7.03 (m, 6H), 7.02-7.00 (m, 1H), 6.95-6.86 (m, 8H), 6.50 (d, J = 7.8 Hz, 6H), 6.41 (m,

1H), 6.30 (m, 1H), 5.45 (m, 1H), 4.60 (t, J = 8.6 Hz, 1H), 2.56 (s, 3H, F2Meppy), 2.40 (s, 3H,

F2Meppy). 31P NMR (CDCl3, 81 MHz): δ 69.29 (q, J = 11.8 Hz, P(OPh)3), −1.99 (s, PPh3). Anal.

Calcd for IrC61N2H46F7O6SP2: C, 55.41; H, 3.51; N, 2.12. Found: C, 55.29; H, 3.54; N, 2.03. TOF

mass: 1174, Ir(F2Meppy)2(PPh3)(P(OPh)3); 912, Ir(F2Meppy)2(P(OPh)3); 864, Ir(F2Meppy)2(PPh3).

IR (KBr, cm-1): 1272, 1162 and 1031 (s, OTf−).

Preparation of [trans-Ir(ppy)(NCMe)(H)(PPh3)2](OTf) (4). A reaction mixture of

[Ir(H)2(NCMe)2(PPh3)2](OTf) (3, 0.10 g, 0.11 mmol) and 2-phenylpyridine (ppyH, 0.05 g, 0.33

mmol) in toluene (10 mL) was refluxed for 3 h and cooled down to 25oC before n-pentane (30 mL)

was added to precipitate white micro-crystals of 4 which were collected by filtration, washed with

n-pentane (3 x 10 mL) and dried under vacuum. The yield was 0.13 g and 95 % based on 4. 1H-

NMR (500 MHz, CDCl3): δ 9.39 (d, J = 4.8 Hz, 1H), 7.47 (t, J = 6.3 Hz, 2H), 7.31-7.16 (m, 32H),

7.01 (m, 1H), 6.82 (t, J = 7.5 Hz, 1H), 6.43 (t, J = 7.5 Hz, 1H), 2.13 (s, Ir-NCCH3, 3H), −16.70 (t, J

= 14.7 Hz, 1H, Ir-H). 31P NMR (CDCl3, 81 MHz): δ 12.58 (s, PPh3). 13C NMR (CDCl3, 125.7

MHz): δ 166.74, 151.58, 145.45, 142.53, 142.18, 136.73, 133.93, 130.39, 129.87, 128.73, 128.29,

124.67, 116.63, 3.60 (s, Ir-NCCH3). HETCOR (1H (500 MHz) 13C (125.7 MHz)): δ 9.39 151.58;

7.47 129.87; 6.82 124.67; 7.01 116.63; 7.31-7.16 142.18, 136.73,133.93, 130.39, 128.29;

2.13 3.60.

Preparation of [trans-Ir(ppy)(-CH=CH(p-C6H4CH3))(NCMe)(PPh3)2)(OTf) (5). A reaction

mixture of 4 (0.10 g, 0.09 mmol) and p-toyl-C≡CH( 0.01 g, 0.09 mmol) in CHCl3 (10 mL) was

stirred at 25 oC for 24 hour before n-pentane (30 mL) was added to precipitate beige micro-crystals

of 5 which were collected by filtration, washed with n-pentane (3 x 10 mL), and dried under

vacuum. The yield was 0.10 g and 90 % based on complex 5. 1H NMR (CDCl3, 500 MHz): δ 9.22

(d, J = 5.5 Hz, 1H), 8.17 (m, 2H), 7.38 (t, J = 6.5 Hz, 2H), 7.05-7.29 (m, 35H) 6.9-6.4 (m, 4H), 2.37

(s, M-CHCH(C6H4-CH3), 3H), 2.12 (s, Ir-NCCH3, 3H). 31P NMR (CDCl3, 81 MHz): δ −8.59 (s,

PPh3). 13C NMR (CDCl3, 125.7 MHz): δ 163.60, 152.29, 147.01, 134.55, 130.37, 139.59, 139.30,

137.61, 129.76, 129.50, 128.77, 128.40, 127.98, 125.80, 124.58, 124.17, 123.39, 118.90, 21.39,

4.34. HETCOR (1H (500 MHz) 13C (125.7 MHz)): δ 9.22 152.29; 8.17 128.77, 125.80;

7.38 124.17, 123.39; 7.05-7.29 128.40; 6.9-6.4 139.30; 2.37 21.39; 2.12 4.34.

Preparation of [trans-Ir(ppy)(ppyH)(H)(PPh3)2](OTf) (6). A reaction mixture of 4 (0.10 g,

0.09 mmol) and 2-phenylpyridine (ppyH, 0.04 g, 0.27 mmol) in 2-ethoxyethanol (10 mL) was

refluxed for 5 h and cooled down to 25oC before n-pentane (30 mL) was added to precipitate white

micro-crystals of 6 which were collected by filtration, washed with n-pentane (3 x 10 mL), and

dried under vacuum. The yield was 0.10 g and 90 % based on complex 6. 1H NMR (CDCl3, 500

MHz) : δ 9.20 (d, J = 4.5 Hz, 1H), 9.01 (d, J = 5.1 Hz, 1H), 8.56 (t, J = 7.5 Hz, 1H), 8.23 (d, J = 8.1

Hz, 1H), 7.85 (t, J = 6.6 Hz, 1H), 7.66 (m, 5H), 7.48 (t, J = 10.2 Hz, 2H), 7.40-7.10 (m, 36H), 6.97

(t, J = 10.2 Hz, 1H), 6.58 (t, J = 10.2 Hz, 1H), −15.49 (t, J =14.7 Hz, 1H, Ir-H ). 31P NMR (CDCl3,

81 MHz): δ 5.96 (s, PPh3).

Identification of p-CH3C6H4CHCH2. After separation of 1 by filtration, the filtrate was

reduced by vacuum evaporation and then was passed through silica column by hexane eluent. MS

m/z (%): 117 (100) [M+−H]

[1] K. A. King, P. J. Spellane, R. J. Watts, J. Am. Chem. Soc. 1985, 107, 1431.

[2] SMART, V 5.05 Software for the CCD Detector System; Bruker Analytical X-ray Systems,

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.

[7] C. S. Chin, M. Oh, G. Won, H. Cho, D. Shin, Bull. Korean Chem. Soc. 1999, 20, 85.

[8] M. Nonoyama, Bull. Chem. Soc. Jpn. 1974, 47, 767.

[9] C.-L. Lee, R. R. Das, J.-J. Kim, Curr. Appl. Phys. 2005, 5, 309.

1H NMR spectrum of [trans-Ir(ppy)2(PPh3)2](OTf) (1) at 500 MHz in CDCl3.

13C NMR spectrum of [trans-Ir(ppy)2(PPh3)2](OTf) (1) at 125.7 MHz in CDCl3.

1H, 13C –2D HETCOR spectrum of [trans-Ir(ppy)2(PPh3)2](OTf) (1) at 1H 500 MHz, 13C 125.7 MHz in CDCl3.

1H NMR spectrum of [trans-Ir(F2ppy)2(PPh3)2](OTf) (1F2) at 300 MHz in CDCl3.

13C NMR spectrum of [trans-Ir(F2ppy)2(PPh3)2](OTf) (1F2) at 75.5 MHz in CDCl3.

1H NMR spectrum of [trans-Ir(F2Meppy)2(PPh3)2](OTf) (1F2Me) at 300 MHz in CDCl3.

13C NMR spectrum of [trans-Ir(F2Meppy)2(PPh3)2](OTf) (1F2Me) at 75.5 MHz in CDCl3.

1H NMR spectrum of [cis-Ir(ppy)2(PPh3)(P(OPh)3)](OTf) (2) at 500 MHz in CDCl3.

13C NMR spectrum of [cis-Ir(ppy)2(PPh3)(P(OPh)3)](OTf) (2) at 125.7 MHz in CDCl3.

1H, 13C –2D HETCOR spectrum of [cis-Ir(ppy)2(PPh3)(P(OPh)3)](OTf) (2) at 1H 500 MHz, 13C 125.7 MHz in CDCl3.

1H NMR spectrum of [cis-Ir(F2ppy)2(PPh3)(P(OPh)3)](OTf) (2F2) at 300 MHz in CDCl3.

1H NMR spectrum of [cis-Ir(F2Meppy)2(PPh3)(P(OPh)3)](OTf) (2F2Me) at 300 MHz in CDCl3.

1H NMR spectrum of [trans-Ir(ppy)(H)(NCCH3)(PPh3)2] + (4) at 500 MHz in CDCl3.

13C NMR spectrum of [trans-Ir(ppy)(H)(NCCH3)(PPh3)2] + (4) at 125.7 MHz in CDCl3.

1H NMR spectrum of [trans-Ir(ppy)(NCMe)(CHCHR)(PPh3)2] + (R = p-CH3C6H4) (5) at 500 MHz in CDCl3.

13C NMR spectrum of [trans-Ir(ppy)(NCMe)(CHCHR)(PPh3)2] + (R = p-CH3C6H4) (5) at 125.7 MHz in CDCl3.

1H NMR spectrum of [trans-Ir(ppy)(ppyH)(H)(PPh3)2](OTf) (6) at 500 MHz in CDCl3

PL decay measurement data

PL decay for [trans-Ir(ppy)2(PPh3)2](OTf) (1)

PL decay for [cis-Ir(ppy)2(PPh3)(P(OPh)3)](OTf) (2)

PL decay for [trans-Ir(F2ppy)2(PPh3)2](OTf) (1F2)

PL decay for [cis-Ir(F2ppy)2(PPh3)(P(OPh)3)](OTf) (2F2)

PL decay for [trans-Ir(F2Meppy)2(PPh3)2](OTf) (1F2Me)

PL decay for of [cis-Ir(F2Meppy)2(PPh3)(P(OPh)3)](OTf) (2F2Me)

Table 1. Crystal data and structure refinement for [trans-Ir(ppy)2(PPh3)2]OTf (1).

Empirical formula C59H50F3IrN2O5P2S

Formula weight 1210.21

Temp., K 233(2)

Crystal size, mm 0.29 x 0.11 x 0.04

Wavelength 0.71073 Å

Crystal system monoclinic

space group C 2/c

Unit cell dimensions

a, b, c (Å) 49.9642(16), 16.3786(5), 35.3374(11)

α, β, γ (deg.) 90, 134.7190(10), 90

V, Å3 20548.2(11)

Z 16

ρ(calc.), mg/m3 1.565

μ, mm-1 2.766

F(000) 9728

θ range for data collection, deg. 1.15 ≤ θ ≤ 28.33

hkl range -65 ≤ h ≤ 66, -21 ≤ k ≤ 21, -47 ≤ l ≤ 47

Reflections collected / unique 105870 / 25579 [R(int) = 0.0558]

Completeness to theta = 28.33 99.9 %

Absorption correction Semi-empirical from equivalents

Max. and min. transmission 0.890 and 0.698

Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 25579 / 4 / 1335

Goodness-of-fit on F2 1.089

Final R indices [I>2sigma(I)] R1 = 0.0378, wR2 = 0.0841

R indices (all data) R1 = 0.0782, wR2 = 0.1060

Largest diff. peak and hole 1.696 and -1.258 e.A-3

Table 2. Crystal data and structure refinement for [cis-Ir(ppy)2(PPh3)(P(OPh)3)](OTf) (2).

Empirical formula C255H184F12Ir4N8O24P8S4

Formula weight 5116.90

Temp., K 173(2)

Crystal size, mm 0.15 x 0.15 x 0.15

Wavelength 0.71073 Å

Crystal system Triclinic

space group P-1

Unit cell dimensions

a, b, c (Å) 11.7023(4), 20.7236(9), 27.5504(11)

α, β, γ (deg.) 106.835(2), 98.317(2), 97.485(2)

V, Å3 6222.3(4)

Z 1

ρ(calc.), mg/m3 1.366

μ, mm-1 2.289

F(000) 2561.4

θ range for data collection, deg. 0.79 ≤ θ ≤ 25.50

hkl range -14 ≤ h ≤ 14, -25 ≤ k ≤ 25, -33 ≤ l ≤ 33

Reflections collected / unique 97337 / 23160 [R(int) = 0.1154]

Completeness to theta = 25.50 100.0 %

Absorption correction Semi-empirical from equivalents

Max. and min. transmission 0.720 and 0.701

Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 23160 / 1 / 1337

Goodness-of-fit on F2 1.062

Final R indices [I>2sigma(I)] R1 = 0.0865, wR2 = 0.2324

R indices (all data) R1 = 0.1363, wR2 = 0.2641

Largest diff. peak and hole 3.861 and -2.200 e.A-3