Published on Web 05/22/2003

Synthesis and Characterization of Facial and Meridional

Tris-cyclometalated Iridium(III) Complexes
Arnold B. Tamayo, Bert D. Alleyne, Peter I. Djurovich, Sergey Lamansky,
Irina Tsyba, Nam N. Ho, Robert Bau, and Mark E. Thompson*
Contribution from the Department of Chemistry, UniVersity of Southern California,
Los Angeles, California 90089-0744
Received February 6, 2003; E-mail: [email protected]

Abstract: The synthesis, structures, electrochemistry, and photophysics of a series of facial (fac) and
meridional (mer) tris-cyclometalated Ir(III) complexes are reported. The complexes have the general formula
Ir(C∧N)3 [where C∧N is a monoanionic cyclometalating ligand; 2-phenylpyridyl (ppy), 2-(p-tolyl)pyridyl (tpy),
2-(4,6-difluorophenyl)pyridyl (46dfppy), 1-phenylpyrazolyl (ppz), 1-(4,6-difluorophenyl)pyrazolyl (46dfppz),
or 1-(4-trifluoromethylphenyl)pyrazolyl (tfmppz)]. Reaction of the dichloro-bridged dimers [(C∧N)2Ir(µ-Cl)2Ir-
(C∧N)2] with 2 equiv of HC∧N at 140-150 °C forms the corresponding meridional isomer, while higher
reaction temperatures give predominantly the facial isomer. Both facial and meridional isomers can be
obtained in good yield (>70%). The meridional isomer of Ir(tpy)3 and facial and meridional isomers of
Ir(ppz)3 and Ir(tfmppz)3 have been structurally characterized using X-ray crystallography. The facial isomers
have near identical bond lengths (av Ir-C ) 2.018 Å, av Ir-N ) 2.123 Å) and angles. The three meridional
isomers have the expected bond length alternations for the differing trans influences of phenyl and pyridyl/
pyrazolyl ligands. Bonds that are trans to phenyl groups are longer (Ir-C av ) 2.071 Å, Ir-N av ) 2.031
Å) than when they are trans to heterocyclic groups. The Ir-C and Ir-N bonds with trans N and C,
respectively, have bond lengths very similar to those observed for the corresponding facial isomers. DFT
calculations of both the singlet (ground) and the triplet states of the compounds suggest that the HOMO
levels are a mixture of Ir and ligand orbitals, while the LUMO is predominantly ligand-based. All of the
complexes show reversible oxidation between 0.3 and 0.8 V, versus Fc/Fc+. The meridional isomers are
easier to oxidize by ca. 50-100 mV. The phenylpyridyl-based complexes have reduction potentials between
-2.5 and -2.8 V, whereas the phenylpyrazolyl-based complexes exhibit no reduction up to the solvent
limit of -3.0 V. All of the compounds have intense absorption bands in the UV region assigned into
1(π f π*) transitions and weaker MLCT (metal-to-ligand charge transfer) transitions that extend to the

visible region. The MLCT transitions of the pyrazolyl-based complexes are hypsochromically shifted relative
to those of the pyridyl-based compounds. The phenylpyridyl-based Ir(III) tris-cyclometalates exhibit intense
emission both at room temperature and at 77 K, whereas the phenylpyrazolyl-based derivatives emit strongly
only at 77 K. The emission energies and lifetimes of the phenylpyridyl-based complexes (450-550 nm,
2-6 µs) and phenylpyrazolyl-based compounds (390-440 nm, 14-33 µs) are characteristic for a mixed
ligand-centered/MLCT excited state. The meridional isomers for both pyridyl and pyrazolyl-based
cyclometalates show markedly different spectroscopic properties than do the facial forms. Isolated samples
of mer-Ir(C∧N)3 complexes can be thermally and photochemically converted to facial forms, indicating that
the meridional isomers are kinetically favored products. The lower thermodynamic stabilities of the meridional
isomers are likely related to structural features of these complexes; that is, the meridional configuration
places strongly trans influencing phenyl groups opposite each other, whereas all three phenyl groups are
opposite pyridyl or pyrazolyl groups in the facial complexes. The strong trans influence of the phenyl groups
in the meridional isomers leads to the observation that they are easier to oxidize, exhibit broad, red-shifted
emission, and have lower quantum efficiencies than their facial counterparts.

Introduction excited-state lifetimes and high luminescent efficiencies. These

properties increase the likelihood of either an energy or an
A significant research effort has focused on the synthesis and
electron-transfer process occurring prior to a radiative or
photophysical characterization of octahedral 4d6 and 5d6 metal
complexes.1 These d6 complexes, particularly the diimine (i.e., (1) (a) Balzani, V.; Scandola, F. Supramolecular Photochemistry; Ellis
bipyridine, phenanthroline) chelates of Ru(II) and Os(II), have Horwood: Chichester, U.K., 1991. (b) Balzani, V.; Credi, A.; Scandola,
F. In Transition Metals in Supramolecular Chemistry; Fabbrizzi, L., Poggi,
been widely used in a variety of photonic applications, including A., Eds.; Kluwer: Dordrecht, The Netherlands, 1994; p 1. (c) Lehn, J.-M.
photocatalysis and photoelectrochemistry.2,3 The attraction of Supramolecular Chemistry-Concepts and Properties; VCH: Weinheim,
Germany, 1995. (d) Bignozzi, C. A.; Schoonover, J. R.; Scandola, F. Prog.
these d6 complexes for such applications comes from their long Inorg. Chem. 1997, 44, 11.
10.1021/ja034537z CCC: $25.00 © 2003 American Chemical Society J. AM. CHEM. SOC. 2003, 125, 7377-7387 9 7377
ARTICLES Tamayo et al.

nonradiative relaxation. The photophysics of related tris-chelate shown that a phenylpyrazolyl-based Ir(III) tris-cyclometalate can
Ir(III) complexes have also been investigated.4-6 These Ir(III) be used as an electron blocking material (preventing electron
complexes have been prepared with either diimine ligands or leakage to the hole-transporting layer) to make highly efficient
cyclometalated ligands, such as 2-phenylpyidinato-C2,N (ppy)5,6 single-dopant white OLEDs.16
and 2,2-thienylpyridinato-C2,N (thpy).6 Complexes with the Metal d6 tris-complexes with asymmetric chelate ligands can
formally monoanionic cyclometalating ligands are isoelectronic have either a facial (fac) or a meridional (mer) configuration.
with the cationic tris-diimine complexes of Ru(II) and Os(II). The photophysical and electrochemical properties of facial and
As compared to Ru(II) and Os(II) complexes, however, the d6 meridional isomers have been investigated for a number of Ru-
Ir(III) complexes exhibit longer excited-state lifetimes, typically (II) complexes having asymmetric diimine ligands.17-21 How-
in the order of microseconds, and higher luminescence efficien- ever, for these cationic Ru(II) diimine complexes, it has been
cies [e.g., φphos (fac-Ir(ppy)3) ) 0.4]7 in fluid solutions. These difficult to achieve control over which isomer is obtained from
properties are due to efficient intersystem crossing between the the synthesis, as well as to isolate and purify a specific
singlet and triplet excited states brought about by the strong isomer.17-20 Moreover, the class of ligands that have been used
spin-orbit coupling of the Ir(III) metal ion. (e.g., pyridyl-pyrazoles) gave only minor differences in the
The photophysical properties of bis- and tris-cyclometalated photophysical properties between the facial and meridional
complexes of Ir(III) make them very useful for several photonic isomers because the two types of coordinating ligand, that is,
applications.4,5a,8-10 These compounds can be employed as pyridyl and pyrazolyl, have very similar electronic and coor-
sensitizers for outer-sphere electron-transfer reactions,11,12 pho- dinating characteristics.17,18 On the other hand, tris-chelates with
tocatalysts for CO2 reduction,13 photooxidants, and singlet cyclometalating ligands such as 2-phenylpyridyl should have
oxygen sensitizers.14 A recent application for these compounds pronounced differences between the facial and meridional
is in the field of organic light-emitting devices (OLEDs), where isomers due to the marked disparity between the formally
they have been used as phosphorescent dopants in the emitting anionic phenyl ligand and neutral pyridyl ligand. To date, all
layer.8b The singlet and triplet excited states that are created investigations into the synthesis and photophysics of tris-
during charge recombination are trapped at the phosphor, where cyclometalated metal d6 complexes have been reported on the
the effective intersystem crossing leads to efficient electrophos- facial isomers,5b,h,6,9a,10 whereas the chemistry of the meridional
phorescence at room temperature.15 Recently, it has also been analogues has remained unexplored. Herein, we describe new
synthetic routes which allow for isolation of either facial or
(2) (a) Kalyanasundaran, K. Coord. Chem. ReV. 1982, 46, 159. (b) Chin, K.- meridional isomers of tris-cyclometalates of Ir(III). The me-
F.; Cheung, K.-K.; Yip, H.-K.; Mak, T. C. W.; Che, C. M. J. Chem. Soc.,
Dalton Trans. 1995, 4, 657. (c) Sonoyama, N.; Karasawa, O.; Kaizu, Y. J.
ridional isomers have been prepared in good yield (ca. >70%)
Chem. Soc., Faraday Trans. 1995, 91, 437. (d) Tan-Sien-Hee, L.; as kinetically favored products. The structures of these com-
Mesmaeker, A. K.-D. J. Chem. Soc., Dalton Trans. 1994, 24, 3651. (e) plexes have been determined by X-ray diffraction and NMR
Kalyanasundaram, K.; Gratzel, M. Coord. Chem. ReV. 1998, 177, 347.
(3) (a) Anderson, P. A.; Anderson, R. F.; Furue, M.; Junk, P. C.; Keene, F. methods. The photophysical properties of both facial and
R.; Patterson, B. T.; Yeomans, B. D. Inorg. Chem. 2000, 39, 2721. (b) Li,
C.; Hoffman, M. Z. Inorg. Chem. 1998, 37, 830. (c) Berg-Brennan, C.; meridional complexes have also been examined and show
Subramanian, P.; Absi, M.; Stern, C.; Hupp, J. T. Inorg. Chem. 1996, 35, distinct differences between the two forms. The meridional
3719. (d) Kawanishi, Y.; Kitamura, N.; Tazuke, S. Inorg. Chem. 1989, 28,
2968. isomers display red-shifted emission and decreased quantum
(4) (a) Balzani, V.; Juris, A.; Venturi, M.; Campagna, S.; Serroni, S. Chem. efficiencies relative to their facial analogues. We also report
ReV. 1996, 96, 759. (b) Shaw, J. R.; Sadler, G. S.; Wacholtz, W. F.; Ryu,
C. K.; Schmehl, R. H. New J. Chem. 1996, 20, 749. on the conversion of the meridional isomers to facial forms by
(5) (a) Sprouse, S.; King, K. A.; Spellane, P. J.; Watts, R. J. J. Am. Chem. both thermal and photochemical routes.
Soc. 1984, 106, 6647. (b) King, K, A.; Spellane, P. J.; Watts, R. J. J. Am.
Chem. Soc. 1985, 107, 1432. (c) Ohsawa, Y.; Sprouse, S.; King, K. A.;
DeArmond, M. K.; Hanck, K. W.; Watts, R. J. J. Phys. Chem. 1987, 91, Experimental Section
1047. (d) Ichimura, K.; Kobayashi, T.; King, K. A.; Watts, R. J. J. Phys.
Chem. 1987, 91, 6104. (e) Garces, F. O.; King, K. A.; Watts, R. J. Inorg. Equipment. UV-visible spectra were measured on an AVIV model
Chem. 1988, 27, 3464. (f) Garces, F. O.; Watts, R. J. Inorg. Chem. 1990, 14DS UV-vis-IR (a reengineered Cary 14) or a Hewlett-Packard 4853
29, 582. (g) Wilde, A. P.; King, K. A.; Watts, R. J. J. Phys. Chem. 1991,
95, 629. (h) Dedeian, K.; Djurovich, P. I.; Garces, F. O.; Carlson, G.; Watts, diode array spectrophotomer. Steady-state emission spectra were
R. J. Inorg. Chem. 1991, 30, 1685. measured with a Photon Technology International QuantaMaster model
(6) (a) Colombo, M. G.; Hauser, A.; Gudel, H. U. Inorg. Chem. 1993, 32, C-60 spectrofluorimeter. Phosphorescence lifetime measurements (>2
3088. (b) Colombo, M. G.; Brunold, T. C.; Riedener, T.; Gudel, H. U.
Inorg. Chem. 1994, 33, 545. µs) were performed on the same fluorimeter equipped with a micro-
(7) (a) Sprouse, S.; King, K. A.; Spellane, P. J.; Watts, R. J. J. Am. Chem. second xenon flash lamp or using an IBH Fluorocube fluorimeter
Soc. 1984, 106, 6647. (b) Crosby, G. A. J. Chim. Phys. 1967, 64, 160.
(8) (a) Lamansky, S.; Djurovich, P.; Murphy, D.; Abdel-Razzaq, F.; Kwong, equipped with a blue LED (λmax ) 373 nm). The quantum efficiency
R.; Tsyba, I.; Bortz, M.; Mui, B.; Bau, R.; Thompson, M. E. Inorg. Chem. (QE) measurements were carried out at room temperature in degassed
2001, 40, 1704. (b) Lamansky, S.; Djurovich, P.; Murphy, D.; Abdel- 2-methyltetrahydrofuran solutions using the optically dilute method.22
Razzaq, F.; Lee, H.; Adachi, C.; Burrows, P. E.; Forrest, S. R.; Thompson,
M. E. Inorg. J. Am. Chem. Soc. 2001, 40, 1704.
(9) (a) Grushin, V. V.; Herron, N.; LeCloux, D. D.; Marshall, W. J.; Petrov, (15) (a) Baldo, M. A.; O’Brien, D. F.; You, Y.; Shoustikov, A.; Sibley, S.;
V. A.; Wang, Y. Chem. Commun. 2001, 1494. (b) Wang Y.; Herron, N.; Thompson, M. E.; Forrest, S. R. Nature 1998, 395, 151. (b) Baldo, M. A.;
Grushin, V. V.; LeCloux, D.; Petrov, V. Appl. Phys. Lett. 2001, 79, 479. Lamansky, S.; Burrows, P. E.; Thompson, M. E.; Forrest, S. R. Appl. Phys.
(10) Ostrowski, J. C.; Robinson, M. R.; Heeger, A. J.; Bazan, G. C. Chem. Lett. 1999, 75, 4. (c) Thompson, M. E.; Burrows, P. E.; Forrest, S. R. Curr.
Commun. 2002, 784. Opin. Solid State Mater. Sci. 1999, 4, 369.
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Res. 1978, 11, 94. Thompson, M. E. New J. Chem. 2002, 1171.
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(13) (a) Belmore, K. A.; Vanderpool, R. A.; Tsai, J.-C.; Khan, M. A.; Nicholas, 1488.
K. M. J. Am. Chem. Soc. 1988, 110, 2004. (b) Silaware, N. D.; Goldman, (18) Steel, P. J.; Constable, E. C. J. Chem. Soc., Dalton Trans. 1990, 1389.
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7378 J. AM. CHEM. SOC. 9 VOL. 125, NO. 24, 2003

Tris-cyclometalated Iridium(III) Complexes ARTICLES

Table 1. Crystallographic Data for mer-Ir(tpy)3, fac-Ir(ppz)3, mer-Ir(ppz)3, fac-Ir(tfmppz)3, and mer-Ir(tfmppz)3
mer-Ir(tpy)3‚CH2Cl2 fac-Ir(ppz)3 mer-Ir(ppz)3 fac-Ir(tfmppz)3 mer-Ir(tfmppz)3
empirical formula C36H30IrN3‚CH2Cl2 C27H21IrN6 C27H21IrN6 C30H18F9IrN6 C30H18F9IrN6
formula weight 781.76 621.70 621.70 825.70 825.70
temperature, K 223(2) 273(2) 296(2) 296(2) 296(2)
wavelength (Å) 0.71073 0.71073 0.71073 0.71073 0.71073
crystal system monoclinic tetragonal monoclinic orthorhombic monoclinic
space group P2(1)/n P-42(1)c P2(1)/c Pbca P2(1)/n
unit cell dimensions
a (Å) 15.113(2) 23.125(11) 15.2907(13) 17.5088(13) 11.5923(10)
b (Å) 9.9696(15) 23.125(11) 14.8863(11) 17.0833(12) 33.878(3)
c (Å) 21.093(3) 8.854(8) 10.1503(9) 40.472(3) 15.5667(14)
R (deg) 90 90 90 90 90
β (deg) 91.383(3) 90 97.607(5) 90 103.030(2)
γ (deg) 90 90 90 90 90
volume (Å3) 3177.2(8) 4735(5) 2290.1(3) 12 105.4(15) 5956.0(9)
Z 4 8 4 16 8
density, calcd (g/cm3) 1.634 1.744 1.803 1.812 1.842
absorption coefficient (mm-1) 4.401 5.667 5.858 4.499 4.572
F(000) 1544 2416 1208 6368 3184
θ range for data collection (deg) 1.64-24.71 1.25-27.56 1.34-28.42 1.01-24.71 1.47-24.71
reflections collected 24 547 27 943 13 642 59 022 30 328
independent reflections 5422 5315 5263 10 321 10 165
[R(int) ) 0.0489] [R(int) ) 0.0484] [R(int) ) 0.0262] [R(int) ) 0.0459] [R(int) ) 0.0313]
refinement method full-matrix least- full-matrix least- full-matrix least- full-matrix least- full-matrix least-
squares on F2 squares on F2 squares on F2 squares on F2 squares on F2
data/restraints/parameters 5219/0/353 5315/0/308 5263/0/143 10 321/108/786 10 165/108/786
goodness-of-fit on F2 1.066 1.054 1.004 1.037 1.023
final R indices [I > 2σ(I)] 0.0521 0.0366 0.0480 0.0495 0.0468
R indices (all data) 0.0686 0.0477 0.0706 0.0731 0.0595

Solutions of coumarin 47 in ethanol (Φ ) 0.60) were used as reference. were input and refined in a riding manner along with the attached
NMR spectra were recorded on Bruker AMX 360 and 500 MHz carbons. All of the structural analyses proceeded smoothly except that
instruments. Mass spectra were taken with a Hewlett-Packard GC/MS of mer-Ir(ppz)3, which was complicated by a slight packing disorder
instrument with electron impact ionization and model 5873 mass of one of the three ppz ligands. This necessitated several data sets to
sensitive detector. Elemental analyses (CHN) were performed at the be collected for mer-Ir(ppz)3 until a crystal was found that yielded a
Microanalysis Laboratory at the University of Illinois, Urbana- satisfactory result. Anisotropic refinement of this data set led to
Champaign. unreasonable bond distances so only the isotropically refined data were
Electrochemistry. Cyclic voltammetry and differential pulsed used in the subsequent analysis. A summary of the refinement details
voltammetry were performed using an EG&G potentiostat/galvanostat and the resulting factors for mer-Ir(tpy)3, fac-Ir(ppz)3, mer-Ir(ppz)3, Ir-
model 283. Anhydrous DMF (Aldrich) was used as the solvent under (tfmppz)3, and mer-Ir(tfmppz)3 are given in Table 1.
inert atmosphere, and 0.1 M tetra(n-butyl)ammonium hexafluorophos- Density Functional Calculations. DFT calculations were performed
phate was used as the supporting electrolyte. A glassy carbon rod was using the Titan software package (Wavefunction, Inc.) at the B3LYP/
used as the working electrode, a platinum wire was used as the counter LACVP** level. The HOMO and LUMO energies were determined
electrode, and a silver wire was used as a pseudoreference electrode. using minimized singlet geometries to approximate the ground state.
The redox potentials are based on values measured from differential The minimized singlet geometries were used to calculate the triplet
pulsed voltammetry and are reported relative to a ferrocene/ferrocenium molecular orbitals and approximate the triplet HSOMO (HSOMO )
(Cp2Fe/Cp2Fe+) redox couple used as an internal reference,23 while highest singly occupied molecular orbital).
electrochemical reversibility was determined using cyclic voltammetry. Synthesis. The compounds 2-(4,6-difluorophenyl)pyridine,26 1-(4,6-
X-ray Crystallography. Diffraction data for mer-Ir(ppz)3, fac-Ir- difluorophenyl)pyrazole,27 and 1-(4-trifluoromethylphenyl)pyrazole27
(tfmppz)3, and mer-Ir(tfmppz)3 were collected at room temperature were prepared following literature procedures. Ir(acac)3 was purchased
(T ) 23 °C), while data for mer-Ir(tpy)3 and fac-Ir(ppz)3 were taken at from Strem Chemical Co., IrCl3‚nH2O was from Next Chimica, and
-50 and 0 °C, respectively. The data sets were collected on a Bruker all other chemicals were purchased from Aldrich Chemical Co. and
SMART APEX CCD diffractometer with graphite monochromated Mo used as received.
KR radiation (λ ) 0.71073 Å). The cell parameters for the Ir complexes
All experiments involving IrCl3‚xH2O or any other Ir(III) species
were obtained from a least-squares refinement of the spots (from 60
were carried out in inert atmosphere despite the stability of the
collected frames) using the SMART program. One hemisphere of crystal
compounds in air, the main concern being their oxidative and thermal
data for each compound was collected up to a resolution of 0.80 Å,
stability of intermediate complexes at the high temperatures used in
and the intensity data were processed using the Saint Plus program.
the reactions. Cyclometalated Ir(III) µ-chloro-bridged dimers of general
All of the calculations for the structure determination were carried out
formula (C∧N)2Ir(µ-Cl)2Ir(C∧N)2 (where C∧N represents a cyclometa-
using the SHELXTL package (version 5.1).24 Absorption corrections
lating ligand) were synthesized by the method reported by Nonoyama,28
were applied by using SADABS.25 In most cases, hydrogen positions
which involves heating IrCl3‚H2O to 110 °C with 2-2.5 equiv of
(22) (a) Demas, J. N.; Crosby, G. A. J. Phys. Chem. 1978, 82, 991. (b) DePriest, cyclometalating ligand in a 3:1 mixture of 2-ethoxyethanol and
J.; Zheng, G. Y.; Goswami, N.; Eichhorn, D. M.; Woods, C.; Rillema, D. deionized water. (C∧N)2Ir(O∧O) (where O∧O represents 2,2,6,6-
P. Inorg. Chem. 2000, 39, 1955.
(23) (a) Gagne, R. R.; Koval, C. A.; Lisensky, G. C. Inorg. Chem. 1980, 19,
2854. (b) Sawyer, D. T.; Sobkowiak, A.; Roberts, J. L., Jr. Electrochemistry (25) Blessing, R. H. Acta Crystallogr. 1995, A51, 33.
for Chemists, 2nd ed.; John Wiley and Sons: New York, 1995; p 467. (26) Lohse, O.; Thevenin, P.; Waldvogel, E. Synlett 1999, 1, 45.
(24) Sheldrick, G. M. SHELXTL, version 5.1; Bruker Analytical X-ray System, (27) Finar, I. L.; Rackham, D. M. J. Chem. Soc. B 1968, 211.
Inc.: Madison, WI, 1997. (28) Nonoyama, M. Bull. Chem. Soc. Jpn. 1974, 47, 767.

J. AM. CHEM. SOC. 9 VOL. 125, NO. 24, 2003 7379

ARTICLES Tamayo et al.

tetramethyl-3,5-heptanedione, dipivaloylmethane - dpm) was prepared fac-Ir(dfppz)3 (Method B): fac-tris(1-(4,6-difluoro-phenylpyra-

by reacting the dimers with 2-2.5 equiv of the chelating diketone and zolato,N,C2′)iridium(III). Yield: 78%. MS: m/z calcd 729.7; found 730.
an equivalent amount of K2CO3 in 1,2-dichloroethane at 90 °C for Anal. Calcd for C27H15F6N6Ir: C, 44.44; H, 2.07; N, 11.52. Found: C,
24 h.8 44.23; H, 1.89; N, 11.28.
Synthesis of fac-Ir(C∧N)3 Complexes. General Procedure. fac- fac-Ir(tfmppz)3 (Method B): fac-tris(1-(4-trifluoromethylphenyl-
Ir(ppz)3, fac-Ir(46dfppz)3, fac-Ir(tfmppz)3. Method A. This method pyrazolato,N,C2′)iridium(III). Yield: 72%. MS: m/z calcd 789.7; found
involves treating Ir(acac)3 (acac ) acetylacetonate) with 3-3.5 equiv 790. Anal. Calcd for C27H18F9N6Ir: C, 43.64; H, 2.20; N, 10.18.
of the appropriate cyclometalating ligand in refluxing glycerol, as Found: C, 43.68; H, 2.01; N, 9.90.
previously described (see eq 1).5h mer-Ir(ppy)3: mer-tris(2-(phenyl)pyridinato,N,C2′)iridium(III). Yield:
fac-Ir(46dfppy)3, fac-Ir(46dfppz)3, fac-Ir(tfmppz)3. Method B. The 75%. MS: m/z calcd 654.8; found 655. Anal. Calcd for C36H30N3Ir:
(C∧N)2Ir(O∧O) complex and 1.2-1.5 equiv of the appropriate cyclom- C, 60.53; H, 3.69; N, 6.42. Found: C, 60.25; H, 3.59; N, 6.46.
etalating ligand were refluxed under inert gas atmosphere in 10 mL of mer-Ir(tpy)3: mer-tris(2-(p-tolyl)pyridinato,N,C2′)iridium(III). Yield:
glycerol for 20-24 h. After the mixture was cooled to room temper- 78%. MS: m/z calcd 696.9; found 697. Anal. Calcd for C36H30N3Ir:
ature, 20 mL of 5% HCl solution was added, and the product was thrice C, 62.05; H, 4.34; N, 6.03. Found: C, 61.59; H, 4.23; N, 6.04.
extracted with 25 mL of CH2Cl2. The organic extracts were combined mer-Ir(46dfppy)3: mer-tris(2-(4,6-difluorophenyl)pyridinato,N,C2′)-
and then dried with anhydrous MgSO4, after which the solvent was iridium(III). Yield: 74%. MS: m/z calcd 762.7; found 763. Anal. Calcd
removed in vacuo. The crude material was then flash chromatographed for C33H18F6N3Ir: C, 51.97; H, 2.38; N, 5.51. Found: C, 50.25; H,
on a silica column using dichloromethane to yield 60-80% product 2.35; N, 5.31.
(see eq 2). mer-Ir(ppz)3: mer-tris(1-phenylpyrazolato,N,C2′)iridium(III). Yield:
fac-Ir(ppy)3, fac-Ir(tpy)3, fac-Ir(ppz)3. Method C. [(C∧N)2IrCl]2 80%. MS: m/z calcd 621.71; found 622. Anal. Calcd for C27H21N6Ir:
complex, 2-2.5 equiv of the appropriate cyclometalating ligand, and C, 52.16; H, 3.40; N, 13.52. Found: C, 51.74; H, 3.13; N, 13.28.
5-10 equiv of K2CO3 were heated to ∼200 °C under inert atmosphere mer-Ir(dfppz)3: mer-tris(1-(4,6-difluorophenyl)pyrazolato,N,C2′)-
in 10 mL of glycerol for 20-24 h. After the mixture was cooled to iridium(III). Yield: 86%. MS: m/z calcd 729.7; found 730. Anal. Calcd
room temperature, 20 mL of deionized H2O was added, and the resulting for C27H15F6N6Ir: C, 44.44; H, 2.07; N, 11.5. Found: C, 44.32; H,
precipitate was filtered off, washed with two portions of methanol, 1.95; N, 11.27.
followed by ether and hexanes. The crude product was then flash mer-Ir(tfmppz)3: mer-tris(1-(4-trifluoromethylphenylpyrazolato,N,C2′)-
chromatographed on a silica column using dichloromethane to yield iridium(III). Yield: 69%. MS: m/z calcd 789.7; found 790. Anal. Calcd
65-80% pure fac-Ir(C∧N)3 (see eq 3). for C27H18F9N6Ir: C, 43.64; H, 2.20; N, 10.18. Found: C, 44.0; H,
Synthesis of mer-Ir(C∧N)3 Complexes. General Procedure. mer- 2.12; N, 9.95.
Ir(ppy)3, mer-Ir(tpy)3, mer-Ir(ppz)3, mer-Ir(46dfppz)3, mer-Ir(tfmppz)3. Isomerization of mer-Ir(C∧N)3 to fac-Ir(C∧N)3. Thermal Isomer-
All of the meridional isomers, except mer-Ir(46dfppy)3, were prepared ization. Samples of mer-Ir(C∧N)3 (100 mg) were refluxed in 10 mL of
by using a modified version of Method C. [(C∧N)2IrCl]2 complex, 2-2.5 glycerol under inert atmosphere for 24 h. After the mixture was cooled
equiv of the appropriate cyclometalating ligand, and 5-10 equiv of to room temperature, 100 mL of deionized H2O was added, and the
K2CO3 were heated to 140-145 °C under inert atmosphere in 10 mL mixture was filtered off and washed with several portions of water
of glycerol for 20-24 h. After the mixture was cooled to room and allowed to dry. The crude product was flashed chromatographed
temperature, distilled water was added, and the resulting precipitate using a silica/dichloromethane column.
was filtered off, washed with two more portions of distilled water, and Photochemical Isomerization. Samples of mer-Ir(C∧N)3 (10-15
air-dried. The crude product was then flash chromatographed on a silica mg) were dissolved in 0.5 mL of d6-DMSO in Young’s NMR tube
column using dichloromethane to give 68-80% (based on the starting (Wilmad Co.). The samples were degassed, and the 1H NMR spectrum
dichloro-bridged dimer) of the pure meridional tris-cyclometalated was taken before and after exposure to UV light. Handheld TLC lamps
complex. (UVP model UVGL-25) positioned face-to-face and covered with
mer-Ir(46dfppy)3. This complex was prepared by dissolving the aluminum foil were the UV source. After 2 h, >95% conversion was
corresponding dimer, 2 equiv of ligand, and K2CO3 in 2-ethoxyethanol observed as verified by 1H NMR spectroscopy.
and heated to 120 °C for overnight. The reaction mixture was then
allowed to cool to room temperature, and the solvent was removed in Results and Discussion
vacuo. The crude product mixture was then flash chromatographed on
Synthesis and Structure of Ir(C∧N)3 Complexes. Tris-
a silica column using dichloromethane to give 74% pure mer-Ir-
(46dfppy)3.
cyclometalated Ir(III) complexes can be prepared by three
Characterization. 1H and 13C NMR chemical shifts and coupling different synthetic routes (eqs 1-3, Scheme 1) using either
constants for all of the complexes listed below are given in the 2-phenylpyridine (ppyH) or 1-phenylpyrazole (ppzH) as the
Supporting Information. cyclometalating ligand precursors (Figure 1). The first method
fac-Ir(ppy)3 (Method C): fac-tris(2-(phenyl)pyridinato,N,C2′)iridium- involves treating Ir(acac)3 with 3 equiv of the free ligand in
(III). Yield: 79%. 1H and 13C NMR spectroscopy and C, H, N analysis glycerol, at refluxing temperatures (Method A, eq 2).5h The tris-
match that reported for fac-Ir(ppy)3.5h cyclometalated complexes can also be prepared from the
fac-Ir(tpy)3 (Method C): fac-tris(2-(p-tolyl)pyridinato,N,C2′)iridium- appropriate β-diketonate derivative [(C∧N)2Ir(O∧O), O∧O )
(III). Yield: 81%. MS: m/z calcd 696.9; found 697. Anal. Calcd for 2,2,6,6-tetramethyl-3,5-heptanedione (dpm)] (Method B) or
C36H30N3Ir: C, 62.05; H, 4.34; N, 6.03. Found: C, 61.67; H, 4.26; N, dichloro-bridged dimer [(C∧N)2Ir(µ-Cl)2Ir(C∧N)2] (Method C),
6.05. by heating the Ir complex with a 2-3-fold excess of cyclo-
fac-Ir(46dfppy)3 (Method B): fac-tris(2-(4,6-difluorophenyl)pyri-
metalating ligand in glycerol. These syntheses work equally well
dinato,N,C2′)iridium(III). Yield: 74%. MS: m/z calcd 762.7; found 763.
for other pyridine-type ligands (e.g., tpyH, 46dfppyH), as well
Anal. Calcd for C33H18F6N3Ir: C, 51.97; H, 2.38; N, 5.51. Found: C,
51.92; H, 2.36; N, 5.51. as for phenylpyrazoles (e.g., 46dfppzH, tfmppzH).
fac-Ir(ppz)3 (Method C): fac-tris(1-phenylpyrazolato,N,C2′)iridium- Methods B and C have several advantages over Method A.
(III). Yield: 84%. MS: m/z calcd 621.7; found 622. Anal. Calcd for The dichloro-bridged dimers28 and (C∧N)2Ir(O∧O)8 compounds
C27H21N6Ir: C, 52.16; H, 3.40; N, 13.52. Found: C, 52.04; H, 3.39; are easily prepared in high yield from IrCl3‚H2O, a starting
N, 13.52. material less expensive than Ir(acac)3. In addition, Methods B
7380 J. AM. CHEM. SOC. 9 VOL. 125, NO. 24, 2003
Tris-cyclometalated Iridium(III) Complexes ARTICLES

Scheme 1

impurity can be readily removed by recrystallization or column

chromatography. Higher yields of the mer-Ir(C∧N)3 complexes
(68-80%) are obtained using Method C at a lower tempera-
ture, that is, 140 °C. Interestingly, different results are obtained
with the fluorine-substituted ligands, 46dfppzH, tfmppzH, and
46dfppyH. All of these ligands give the facial isomer as the
major product when Methods A or B are used at high
temperature (>200 °C). However, when using Method C, we
found that 46dfppzH and tfmppzH give meridional isomers as
principal products, whereas 46dfppyH gives mixtures of fac/
mer-isomers, along with other unidentified products, even at
140 °C. Therefore, pure samples of mer-Ir(46dfppy)3 were
prepared by Method C using 2-ethoxyethanol as solvent at
120 °C.
The coordination geometry of the precursor complexes used
in Method C [(C∧N)2Ir(µ-Cl)2Ir(C∧N)2] has the Ir-N bonds in
a mutually trans disposition. This suggests that cyclometalation
by the third C∧N ligand leads directly to the formation of the
meridional isomer, as observed when the syntheses are carried
out at a lower temperature.5b When the reaction temperature
for Method C is raised to >200 °C, however, isomerization of
either the starting materials or the formed meridional isomers
needs to occur to form the observed facial products (Vide infra).
NMR Characterization. The solution structures of the
complexes were established using 1H, 13C, and, where ap-
plicable, 19F NMR spectroscopy. The 1H and 19F NMR spectra
of fac- and mer-Ir(46dfppz)3 are presented in Figure 2; the 1H
Figure 1. Cyclometalating ligands used to prepare Ir(C∧N)3. Abbreviations
NMR spectra of all of the other complexes are given in the
used throughout the paper are listed below the C∧N fragment.
Supporting Information. The facial and meridional isomers of
and C give higher yields than does Method A. For example, Ir(C∧N)3 complexes are readily distinguished by NMR spec-
reactions using Method C and either ppyH or ppzH give yields troscopy, as all of the derivatives display similar spectral
between 80 and 85% (based on the starting dimer, reaction characteristics. In the facial tris-cyclometalates, the three ligands
temperature ∼200 °C) versus 45-60% using Method A.5h,16 surrounding the iridium atom are magnetically equivalent due
Previous routes to make tris-cyclometalated Ir(III) complexes to the inherent C3 symmetry of the complexes. This gives rise
also utilize either IrCl3‚H2O or (C∧N)2Ir(µ-Cl)2Ir(C∧N)2 com- to first-order NMR spectra and makes spectral interpretation
plexes as starting materials.6,9a However, these methods employ for these isomers relatively straightforward because the total
a large excess of the cyclometalating precursor ligands as number of resonances in the complex are equal to the number
solvent, making it necessary to prepare the desired HC∧N of resonances in a single anionic C∧N ligand. In the 1H NMR
compounds on a relatively large scale. spectrum of fac-Ir(46dfppz)3, for example, five distinct aromatic
The reaction temperature and nature of the cyclometalating proton resonances are displayed, each peak integrating to three
ligand strongly affect the facial/meridional product ratios of the equivalent H’s that correspond to an individual aromatic proton
reactions. For the nonfluorinated ligands ppyH, tpyH, and ppzH, in the 46dfppz ligand (Figure 2). In contrast, the C1 symmetry
both Methods B and C give the facial isomer as the predominant of the mer-Ir(C∧N)3 complexes gives rise to non-first-order 1H
product when reaction temperatures are >200 °C. A small NMR spectra with the total of number of resonances equal to
amount of the meridional isomer (typically 1-3%) is sometimes the total number of aromatic protons in the complex. Hence,
also present in the crude reaction mixture. The meridional the 1H NMR spectrum of the mer-Ir(46dfppz)3 is more com-

J. AM. CHEM. SOC. 9 VOL. 125, NO. 24, 2003 7381

ARTICLES Tamayo et al.

Table 2. Comparison of Selected Bond Distances (Å) for

fac-Ir(tpy)3, (tpy)2Ir(acac),8a and mer-Ir(tpy)3
bond distances (Å)
bond type fac-Ir(tpy)3 mer-Ir(tpy)3 (tpy)2Ir(acac)
Ir-N1
Ir-N2
Ir-N3
} 2.132(5)
2.151(9)
2.044(8)
2.065(8)
2.023(5)
2.040(5)
Ir-C1
Ir-C2
Ir-C3
} 2.024(6)
2.076(10)
2.086(12)
2.020(8)
1.985(7)
1.982(6)

to reported values for other mononuclear complexes with the

(C∧N)2Ir fragment.30,31
Figure 3 gives molecular plots for fac-Ir(tpy)3, mer-Ir(tpy)3,
and (tpy)2Ir(acac). The Ir-C and Ir-N bond lengths for each
of the complexes are given in Table 2. The structural data for
fac-Ir(tpy)329 and (tpy)2Ir(acac)8a were taken from literature
references. The facial isomer sits on a three-fold axis, leading
to identical Ir-C and Ir-N bond lengths of 2.024(6) and 2.132-
(5) Å, respectively. The bond lengths in the meridional isomer
of tpy differ markedly from those of the facial isomer. The Ir-C
bond trans to a pyridyl group (Ir-C3 ) 2.020(8) Å) shares an
electronic environment and, thus, bond length similar to those
of the Ir-C bonds of the facial isomer. Likewise, the Ir-N
bond trans to the phenyl group (Ir-N1 ) 2.151(9) Å) is nearly
the same length as the Ir-N bonds of the facial isomer. The
Ir-N bonds of the mutually trans pyridyl groups in the
meridional complex (Ir-N2 ) 2.044(8) Å and Ir-N3 ) 2.065-
(8) Å) are significantly shorter than Ir-N bonds of the facial
Figure 2. 1H and 19F NMR spectra of fac-Ir(46dfppz)3 (top) and mer-Ir- isomer. This is consistent with the weaker trans influence of a
(46dfppz)3 (bottom). The solvent peak is indicated by *. The 19F spectra pyridyl group relative to a phenyl ligand.32 In contrast, the Ir-C
(C6F6 was used as an external reference δ (ppm): -164 ppm) are shown as
insets to the 1H spectra. The 19F spectrum of the meridional isomer is shown bonds trans to phenyl groups (Ir-C1 ) 2.076(10) Å and Ir-
with a split scale for clarity. C2 ) 2.086(12) Å) have lengths markedly longer than the Ir-C
bonds of the facial isomer, consistent with the significant trans
plicated than the facial isomer with 15 distinct aromatic proton influence of phenyl groups on each other. It is also interesting
resonances appearing in the spectrum, each integrating as a to compare mer-Ir(tpy)3 and (tpy)2Ir(acac) structures. The bis-
single proton. For example, three aromatic resonances in the cyclometalated fragment of (tpy)2Ir(acac) has the same disposi-
facial isomer, labeled Ha, Hc, and He (δ ) 8.30, 6.9, 6.2 ppm, tion of tpy ligands as found in mer-Ir(tpy)3, and the mutually
respectively), appear as nine separate resonances in the meridi- trans disposed Ir-N bonds in both complexes lengths have
onal isomer. Similarly, the 1H-decoupled 13C NMR spectrum similar lengths. On the other hand, the weak trans influence of
of fac-Ir(46dfppz)3 displays only nine inequivalent aromatic the acetylacetonate ligand leads to shorter Ir-C bonds (av )
carbon resonances, whereas 27 carbon resonances are observed 1.984(6) Å) for the (tpy)2Ir(acac) complex than those observed
for the meridional isomer. The 19F NMR spectroscopy also in either the meridional or the facial Ir(tpy)3 complexes.
clearly distinguishes between the isomers of Ir(dfppz)3 (see insets The structures of the facial and meridional isomers of Ir-
to Figure 2). The facial isomer shows two distinct fluorine (ppz)3 are shown in Figure 4. The Ir-C and Ir-N bond lengths
resonances, while the meridional isomer displays six distinct for the two complexes are given in Table 3. The average Ir-C
fluorine resonances. (2.021(6) Å) and Ir-N (2.124(5) Å) bond lengths of fac-Ir-
X-ray Crystallography. Single crystals of mer-Ir(tpy)3, as (ppz)3 are very similar to those of fac-Ir(tpy)3, suggesting a
well as the facial and meridional isomers of Ir(ppz)3 and Ir- similar trans influence for pyridyl and pyrazolyl groups. In the
(tfmppz)3, were grown from methanol/dichloromethane solution meridional isomer, the mutually trans Ir-C bond lengths (Ir-
and characterized using X-ray crystallography. The crystal data C1 and Ir-C2, av ) 2.054(2) Å) are similar to those of mer-
are given in Table 1. Tables of atomic coordinates, bond lengths, Ir(tpy)3 and reflect an equivalent degree of trans influence for
and angles for each complex are given in the Supporting both aryl groups in the two chelate systems. The mutually trans
Information. All of the complexes examined here (both fac- and Ir-N bond lengths (Ir-N1 and Ir-N2, av ) 2.019(2) Å) are
mer-isomers) have the three cyclometalating ligands in a
pseudooctahedral coordination geometry around the metal (29) Garces, F. O.; Dedian, K.; Keder, N. L.; Watts, R. J. Acta Crystallogr.
center. The C-C and C-N intraligand bond lengths and angles 1993, C49, 1117.
(30) Urban, R.; Kramer, R.; Mihan, S.; Polborn, K.; Wagner, B.; Beck, W. J.
are within normal ranges expected for cyclometalated Ir(III) Organomet. Chem. 1996, 517, 191.
complexes and are similar to values reported for the (C∧N)2Ir- (31) Neve, F.; Crispini, A. Eur. J. Inorg. Chem. 2000, 1039.
(32) Douglas, B.; McDaniel, D.; Alexander, J. Concepts and Models in Inorganic
(µ-Cl)2Ir(C∧N)2)29 and fac-Ir(C∧N)39a,29 complexes, as well as Chemistry, 3rd ed.; John Wiley & Sons, Inc.: New York, 1994.

7382 J. AM. CHEM. SOC. 9 VOL. 125, NO. 24, 2003

Tris-cyclometalated Iridium(III) Complexes ARTICLES

Figure 3. ORTEP drawings of fac-Ir(tpy)3, mer-Ir(tpy)3, and (tpy)2Ir(acac). The thermal ellipsoids for the image represent 25% probability limit. The
hydrogen atoms have been omitted for clarity.

Figure 4. ORTEP drawings of (a) fac-Ir(ppz)3, (b) mer-Ir(ppz)3, (c) fac-Ir(tfmppz)3, and (d) mer-Ir(tfmppz)3.

Table 3. Selected Bond Distances (Å) and Angles (deg) for well as to the Ir-C and Ir-N bonds in the facial isomer. This
fac-Ir(ppz)3, mer-Ir(ppz)3, fac-Ir(tfmppz)3, and mer-Ir(tfmppz)3
decrease in bond distance is most likely due to less steric
Ir(ppz)3 Ir(tfmppz)3 repulsion between the ppz ligands when the complex is in a
bond type facial meridional facial meridional meridional configuration.
Bond Distances (Å) The structures of the facial and meridional isomers of Ir-
Ir-N1 2.117(5) 2.053(2) 2.114(7) 2.095(4) (tfmppz)3 are shown in Figure 4, and the Ir-C and Ir-N bond
Ir-N2 2.135(5) 2.026(2) 2.113(7) 2.024(5)
Ir-N3 2.120(6) 2.013(2) 2.116(8) 2.016(5) lengths are given in Table 3. The electron-accepting trifluo-
Ir-C1 2.015(7) 2.051(2) 2.016(8) 2.073(5) romethyl group of the tfmppz ligand is in a meta disposition
Ir-C2 2.027(6) 2.057(2) 2.016(8) 2.083(5) relative to Ir and, electronically, is thus weakly coupled to the
Ir-C3 2.021(6) 1.993(2) 2.013(8) 1.991(5) metal center. Hence, the average Ir-C (2.015(8) Å) and Ir-N
Bond Angles (deg) (2.114(7) Å) bond lengths for the facial Ir(tfmppz)3 are the same
N2-Ir-N3 94.4(2) 171.54(8) 95.1(3) 171.26(17)
C1-Ir-C2 93.7(3) 172.67(9) 93.7(3) 170.9(2)
as those observed for the facial isomers of both Ir(tpy)3 and
Ir(ppz)3. For the meridional isomer of Ir(tfmppz)3, the mutually
trans Ir-C bonds (av ) 2.078(5) Å) and Ir-N bonds (av )
also similar to values for the corresponding bonds in mer-Ir- 2.020(5) Å) are similar in length to the equivalent bonds in mer-
(tpy)3 consistent with pyrazole having a trans influence com- Ir(tpy)3 and mer-Ir(ppz)3. The Ir-C trans to pyrazolyl (1.991-
parable to that of pyridine. However, the bond lengths for Ir-C (5) Å) and Ir-N trans to phenyl (2.095(4) Å) bond lengths are
trans to pyrazolyl (1.993(2) Å) and Ir-N trans to phenyl (2.053 also similar to values for the corresponding bonds in the
Å) are shorter than the corresponding pair in mer-Ir(tpy)3, as meridional tpy and ppz complexes. Likewise, the bond distances

J. AM. CHEM. SOC. 9 VOL. 125, NO. 24, 2003 7383

ARTICLES Tamayo et al.

Table 4. Photophysical and Electrochemical Properties of Ir(C∧N)3 Complexes

complex absorptiona emission at 77 Kb emission at 298 K redox (V)c
Ir(C∧N)3 λ (nm) {, 103 L mol-1 cm-1} λmax τ (µs) λmax τ (µs) E1/2ox E1/2red
ppy
fac 244 (45.5), 283 (44.8), 341 (9.2), 377 (12.0), 405 (8.1), 455 (2.8), 488 (1.6) 492 3.6 510 1.9 0.31 -2.70, -3.00
mer 246 (47.3), 276 (51.0), 339 (9.2), 382 (10.7), 410 (7.2), 457 (3.4), 488 (1.4) 493 4.2 512 0.15 0.25 -2.63, -2.82
tpy
fac 248 (41.4), 287 (44.7), 347 (10.6), 374 (11.8), 410 (7.0), 450 (2.9), 485 (1.4) 492 3.0 510 2.0 0.30 -2.78, -3.09
mer 276 (53.6), 336 (13.4), 383 (8.4), 420 (5.3), 451 (3.7), 485 (1.5) 530d 4.8 550 0.26 0.18 -2.73, -3.04
46dfppy
fac 240 (50.2), 274 (44.7), 292 (25.5), 346 (11.3), 379 (7.1), 427 (1.6), 457 (0.3) 450 2.5 468 1.6 0.78 -2.51, -2.81
mer 264 (50.7), 312 (15.5), 353 (8.8), 388 (7.8), 428 (2.5), 456 (0.9) 460 5.4 482 0.21 0.69 -2.50, -2.86
ppz
fac 244 (49.1), 261 (41.1), 292 (16.5), 321 (13.5), 366 (4.2) 414 14 0.39
mer 228 (44.8), 246 (44.0), 293 (17.3), 320 (9.6), 349 (5.1) 427d 28 0.28
46dfppz
fac 246 (55.3), 254 (49.9), 283 (23.1), 316 (10.0) 390d 27 0.80
mer 244 (48.0), 278 (24.0), 322 (8.9) 402d 33 0.72
tfmppz
fac 243 (45.3), 251 (40.8), 261 (37.0), 289 (12.2), 323 (10.6), 364 (3.6) 422 17 428 0.05 0.73
mer 234 (42.3), 247 (46.6), 287 (19.4), 344 (7.7), 372 (3.2) 430d 32 0.62

a Absorption measurements of complexes were taken in CH Cl . b 77 K emission and lifetime measurements were carried out in 2-methyltetrahydrofuran.
2 2
cRedox measurements were carried out in anhydrous DMF solution; values are reported relative to Cp2Fe/Cp2Fe+. d The λmax values correspond to the
highest energy peak in the spectrum. See Supporting Information.

for the trans disposed phenyl and pyrazolyl groups are relatively These values are in close agreement with the data obtained from
unperturbed by the CF3 substituent. photophysical measurements (vide infra). The calculation results
DFT Calculations. B3LYP density functional theory (DFT) for other tris-cyclometalated Ir complexes will be discussed in
calculations were carried out on all of the Ir(C∧N)3 complexes the following text as they pertain to electrochemical and spectral
using the Titan software package (Wavefunction, Inc.) with a interpretation.
LACVP** basis set. A similar approach has been used to Electrochemistry. The electrochemical properties of the tris-
investigate the ground- and excited-state properties of cyclo- cyclometalated iridium complexes were examined by cyclic
metalated Ir and Pt compounds.33,34 The HOMO and LUMO voltammetry. A summary of the redox potentials, measured
surfaces for fac- and mer-Ir(ppz)3 are illustrated in the Sup- relative to an internal ferrocene reference (Cp2Fe/Cp2Fe+ )
porting Information. The discussion here will focus on the results 0.45V vs SCE in DMF solvent),23 is given in Table 4. All of
for fac- and mer-Ir(ppz)3; however, all of the examined facial the complexes show reversible oxidation, with potentials of
and meridional isomers give a similar picture for the HOMO 0.30-0.80 V. The phenylpyridyl-based derivatives exhibit
and LUMO orbitals. The calculated values for the Ir-C (2.17 reversible reduction, in the range from -2.51 to -2.78V.
Å) and Ir-N (2.04 Å) bond distances and N-Ir-N (96.3°) and However, no reduction is observed for the phenylpyrazolyl-
C-Ir-C (95.2°) bond angles are comparable to the experimental based complexes out to -3.0 V (the solvent limit in DMF).
values determined in the X-ray structure of fac-Ir(ppz)3 (see The DFT calculations suggest that the reductive process is
Table 3). Likewise, the calculated Ir-C and Ir-N bond lengths largely localized on the heterocyclic portion of the cyclometa-
of mer-Ir(ppz)3 have the same length alternations as those lating ligands. The reductive electrochemistry of the Ir(C∧N)3
observed in the X-ray structure. The calculated HOMO energies complexes is thus consistent with the pyrazolyl being signifi-
for fac- and mer-Ir(ppz)3 are -5.02 and -4.81 eV, respectively. cantly more difficult to reduce than a pyridyl group. The absence
The HOMO pictures for both isomers consist of a mixture of of reductive processes in pyrazolyl ligated complexes is a
phenyl and Ir orbitals. The HOMO in the fac-isomer is common occurrence noted by other research groups.35-38 For
distributed equally among the three ppz ligands due to the C3 example, neither Pt(II) nor Rh(III) phenylpyrazolyl cyclometa-
symmetry of the complex. The HOMO of the mer-isomer is lates undergo measurable reduction, unlike the phenylpyridyl
localized primarily on the two ppz ligands with the transoid analogues.6,34
disposition of nitrogen. Similarly, the LUMO - while predomi- Replacing the pyridyl moiety with a pyrazolyl group also
nantly phenylpyrazolyl in character - is delocalized among the affects the oxidation potentials of the metal complexes. The
three ligands in the fac-isomer (-0.57 eV) as opposed to being oxidation potential of fac-Ir(ppz)3 (0.39 V) is shifted to a slightly
localized on a single ligand in the mer-isomer (-0.60 eV). The higher potential than that of fac-Ir(ppy)3 (0.31 V). The DFT
triplet HSOMOs (HSOMO ) highest singly occupied molecular calculations show that the HOMOs of all of the tris-cyclom-
orbital) are calculated to be -1.60 and -1.53 eV for the fac- etalated complexes examined here are composed of Ir-d and
and mer-isomer, respectively. The triplet state energy can then phenyl-π orbitals, similar to related studies.33 While the pyridyl
be estimated as the difference between the ground-state singlet and pyrazolyl ligands do not contribute markedly to the HOMO,
(HOMO) and triplet (HSOMO) energies.33,34 The values ob-
(35) Sandrini, D.; Maestri, M.; Ciano, M.; Balzani, V.; Lueoend, R.; Deuschel-
tained for the theoretical triplet energy are 3.42 eV (362 nm) Cornioley, C.; Chassot, L.; Von Zelewsky, A. Gazz. Chim. Acta 1988, 118,
for fac-Ir(ppz)3 and 3.28 eV (378 nm) for the meridional isomer. 661.
(36) Maeder, U.; Stoeckli-Evans, H.; von Zelewsky, A. HelV. Chim. Acta 1992,
73, 1321.
(33) Hay, P. J. J. Phys. Chem. A. 2002, 106, 1634. (37) Sandrini, D.; Maestri, M.; Ciano, M.; Maeder, U.; von Zelewsky, A. HelV.
(34) Brooks, J.; Babayan, Y.; Lamansky, S.; Djurovich, P. I.; Tsyba, I.; Bau, Chim. Acta 1990, 73, 1307.
R.; Thompson, M. E. Inorg. Chem. 2002, 41, 3055. (38) Chassot, L.; von Zelewsky, A. Inorg. Chem. 1987, 26, 2814.

7384 J. AM. CHEM. SOC. 9 VOL. 125, NO. 24, 2003

Tris-cyclometalated Iridium(III) Complexes ARTICLES

they do affect the energies of the metal orbitals through π-back-

bonding. Previous studies with neutral pyrazole ligands and
deprotonated pyrazoles have indicated that the pyrazolyl ligands
are weak π-acceptors similar to pyridyl ligands.19,39 A similar
observation has been reported for analogous Pt complexes;
Pt(phpz)2 has a higher oxidation potential than Pt(ppy)2 (0.49
and 0.26 V, respectively).38 In accord with other studies, fluoro
and/or trifluoromethyl substituents also increase the oxidation
potential of the complexes while simultaneously making the
phenylpyridyl-based derivatives easier to reduce.5h,9,34
The meridional tris-cyclometalates have oxidation potentials
ca. 50-100 mV less positive than their facial isomers, while
the reduction potentials for the mer-phenylpyridyl-based com-
plexes are only slightly less negative than those in the
fac-analogues. As mentioned above, the oxidation processes
involve the Ir-phenyl center, while reduction occurs primarily
on the heterocyclic portion of the C∧N ligands.40 The difference
in electrochemical behavior between the meridional and facial
isomers can be explained by the presence of mutually trans
phenyl ligands in the mer-isomers. This configuration leads to
a lengthening of the transoid Ir-C bonds and, consequently,
destabilizes the HOMO to a significant extent, while only
slightly stabilizing the LUMO. The electrochemistry is in
accordance with results from DFT calculations that suggest that
the HOMO energies of the meridional isomers are higher than
those of the facial forms, while the LUMO energies are roughly
the same. For example, the calculated HOMO energy for mer-
Ir(tpy)3 is -4.67 versus -4.78 eV for fac-Ir(tpy)3, while the
LUMO energies are less strongly perturbed (-1.18 versus -1.12
eV, respectively). Therefore, on the basis of these calculations,
we predicted that it should be easier to both oxidize and reduce Figure 5. Absorption and emission spectra for facial and meridional isomers
mer-Ir(tpy)3 than would be the case for fac-Ir(tpy)3, as is indeed of Ir(tpy)3 (top) and Ir(ppz)3 (bottom). The absorption spectra were measured
observed. in CH2Cl2 at room temperature, and the emission spectra were measured at
77 K in 2-methyltetrahydrofuran (2-MeTHF) glass.
Electronic Spectroscopy. The absorption and emission
spectra were recorded for all of the complexes. These data are
allowed 1(π f π*) transitions of the phenylpyrazolyl-based
summarized in Table 4, and spectra for fac/mer-Ir(tpy)3 and fac/
ligands.41 These bands, as in the phenylpyridyl-based analogues,
mer-Ir(ppz)3 are given in Figure 5. The photophysical properties
are also accompanied by weaker, low-lying charge-transfer
of the facial isomers of the phenylpyridyl-based Ir(III) cyclo-
transitions at 350-380 nm. However, the MLCT transitions of
metalates have been examined by a number of research
the phenylpyrazolyl-based complexes are significantly higher
groups.5,6,9 The absorption spectra of these compounds show
in energy than those of phenylpyridyl analogues. A similar
intense bands appearing in the ultraviolet part of the spectrum
hypsochromic shift has also been observed in the absorption
between 240 and 350 nm. These bands have been assigned to
spectra of phenylpyrazolyl-based Rh36,37 and Pt35,38 cyclometa-
the spin-allowed 1(π f π*) transitions of the phenylpyridyl
lates, as well as in pyridylpyrazolyl-based Ru tris-chelates.18,19
ligand. The 1(π f π*) bands are accompanied by weaker, lower
The shift to higher energy indicates an increase in energy
energy features extending into the visible region from 350 to
separation between the metal d- and π*-orbitals and is princi-
450 nm that have been assigned to both allowed and spin-
pally due to the fact that the π*-orbitals of pyrazole are higher
forbidden MLCT transitions. The high intensity of these MLCT
in energy than the π*-orbitals of pyridine.18,19,39
bands has been attributed to an effective mixing of these charge-
The facial isomers of the phenylpyridyl-based complexes are
transfer transitions with higher lying spin-allowed transitions
all intensely luminescent, both at 77 K and at room temperature
on the cyclometalating ligand.6 This mixing is facilitated by
(Table 4), with emission characteristic of phosphorescence from
the strong spin-orbit coupling of the Ir(III) center. The
a mixed-ligand-centered-MLCT (LC-MLCT) triplet state.6,8,34
absorption spectra for all of the phenylpyrazolyl-based Ir
The photophysical properties of fac-Ir(tpy)3 at 77 K (λmax )
complexes investigated here also show intense bands appearing
492 nm, τ ) 3.0 µs) are nearly the same as those of fac-Ir-
in the ultraviolet part of the spectrum between 240 and 350
(ppy)3, while the difluoro-substituted analogue, fac-Ir(46dfppy)3,
nm. The measured energies and extinction coefficients are
has a blue-shifted emission (λmax ) 450 nm, τ ) 2.5 µs). The
comparable to those of the free ligands, that is, ppzH, 46dfppzH,
and tfmppzH. Thus, these features are similarly assigned to the (41) (a) Pavlik, J. W.; Connors, R. E.; Burns, D. S.; Kurzweil, E. M. J. Am.
Chem. Soc. 1993, 115, 7645. (b) Cativiela, C.; Laureiro, J. I. G.; Elguero,
(39) Sullivan, P.; Salmon, D. J.; Meyer, T. J.; Peeding, J. Inorg. Chem. 1979, J.; Elguero, E. Gazz. Chim. Ital. 1991, 121, 477. (c) Cativiela, C.; Laureiro,
18, 3369. J. I. G.; Elguero, J.; Elguero, E. Gazz. Chim. Ital. 1989, 119, 41. (d)
(40) Kulikova, M.; Balashev, K. P.; Kvam, P. I.; Songstad, J. Russ. J. Gen. Cativiela, C.; Laureiro, J. I. G.; Elguero, J.; Elguero, E. Gazz. Chim. Ital.
Chem. 2000, 70, 163. 1986, 116, 119.

J. AM. CHEM. SOC. 9 VOL. 125, NO. 24, 2003 7385

ARTICLES Tamayo et al.

large hypsochromic shift caused by 4,6-difluoro substitution is Table 5. Luminescent Quantum Efficiencies, Lifetimes, and the
Radiative/Nonradiative Decay Rates for Ir(C∧N)3 Complexes at
consistent with behavior seen in Pt(II) cyclometalates.34 Sub- Room Temperature
stitution of the phenyl hydrogens with inductively electron-
complex ΦPL τ (µs) kr knr
withdrawing fluorine atoms, particularly on the 4′- and 6′-
positions, stabilizes the HOMO more than the LUMO, thus fac-Ir(ppy)3 0.40 1.9 2.1 × 105 3.2 × 105
mer-Ir(ppy)3 0.036 0.15 2.4 × 105 6.4 × 106
increasing the triplet energy gap.34 fac-Ir(tpy)3 0.50 2.0 2.5 × 105 2.5 × 105
In contrast to the phenylpyridyl-based complexes, the facial mer-Ir(tpy)3 0.051 0.26 2.0 × 105 3.6 × 106
isomers of the phenylpyrazolyl-based compounds are all very fac-Ir(46dfppy)3 0.43 1.6 2.7 × 105 3.6 × 105
mer-Ir(46dfppy)3 0.053 0.21 2.5 × 105 4.5 × 106
weak emitters at room temperature (Φ < 0.1%), but are
intensely luminescent at 77 K. Several related ppz cyclometa-
lated Pt and Rh complexes have also been reported to be poorly processes could involve bond dissociation in the excited state.
emissive in fluid solution but highly emissive in glassy matrixes The mutually trans Ir-C1 and Ir-C2 bonds in the mer-Ir(tpy)3
at 77 K.35,36 The highly structured emissions of the facial are already significantly longer than those of the facial analogue
phenylpyrazolyl-based complexes occur at higher energies and as a result of the strong trans influence of phenyl groups. The
have longer lifetimes than the phenylpyridyl-based analogues. broadened emission of the mer-isomers indicates that the
For example, at 77 K, the emission for fac-Ir(ppz)3 has a excited-state geometry is further distorted from that of the
λmax ) 414 nm and τ ) 14 µs, while for fac-Ir(ppy)3, the values ground state. Photolytic cleavage of either an Ir-C or an Ir-N
are λmax ) 492 nm and τ ) 3.6 µs. The behavior is consistent bond can then lead to subsequent rearrangement of the complex.
with a strongly perturbed ligand-centered transition in the This sort of bond breaking in the excited state is most likely
phenylpyrazolyl derivatives. The triplet energy of the C∧N ligand responsible for the photoisomerization process described below.
strongly influences the phosphorescence energy of the corre-
mer-to-fac Isomerization. The fact that the meridional Ir-
sponding cyclometalate because the excited state has both
(C∧N)3 isomers can be obtained in good yield at low temper-
MLCT and intraligand (π f π*) triplet character.6,8 The triplet
ature, via synthetic Method C, suggests that the meridional
energy of phenylpyrazole (378 nm, 26 500 cm-1)36,41 is greater
isomers are kinetically favored products, while the facial
than that of phenylpyridine (430 nm, 23 300 cm-1);42 therefore,
isomers, obtained at higher temperatures, are thermodynamically
a phenylpyrazolyl-based cyclometalate is expected to have a
favored. To test this hypothesis, the thermal conversion of
higher emission energy than a related phenylpyridyl-based
meridional to facial isomers was examined. A pure sample of
complex. Also, as seen with the phenylpyridyl-based com-
mer-Ir(tpy)3 was dissolved in glycerol and refluxed for 24 h.
plexes,5,34 addition of electron-withdrawing fluorine substituents
Subsequent purification by column chromatography, under
on the phenyl ring of ppz blue-shifts the emission for the
conditions where the facial and meridional isomers are cleanly
corresponding cyclometalated complexes; thus, the triplet energy
separated, gave only a single colored band, and pure fac-Ir-
of fac-Ir(46dfppz)3 is 390 nm. To our knowledge, this is the
(tpy)3 was isolated in >70% yield. This result supports the
first Ir(III) tris-cyclometalate that emits in the ultraviolet region
hypothesis that the meridional isomer is the kinetically favored
(below 400 nm).
product and converts to the facial isomer during high-temper-
The meridional isomers of the tris-cyclometalates exhibit ature synthesis. The mer-Ir(ppy)3, mer-Ir(ppz)3, mer-Ir(46dfppz)3,
photophysical characteristics different from those of their facial and mer-Ir(tfmppz)3 complexes also isomerize to their facial
analogues. For example, the 1(π f π*) absorption in mer-Ir- forms using the same reaction conditions. However, the mer-
(tpy)3 (Figure 5a) occurs as a single intense band at 276 nm, Ir(46dfppy)3 complex did not isomerize under these conditions,
whereas in fac-Ir(tpy)3 it appears as two features at 248 and indicating that a larger kinetic barrier needs be overcome to
287 nm. Likewise, the MLCT band shapes in the meridional isomerize this derivative.
isomer are less sharply defined and have lower extinctions than
The large nonradiative rate constants determined for some
those in the facial isomer. Greater differences exist in the
of the mer-isomers suggest that a bond rupture process may
luminescent behavior. Unlike the highly structured emission
occur in the excited state; hence, the photostability of mer-Ir-
displayed by fac-isomers, the mer-isomers display broader, red-
(C∧N)3 complexes was also examined. The 1H NMR spectra of
shifted luminescence. At room temperature, the mer-isomers
the samples of the meridional complexes in degassed DMSO-
of the phenylpyridyl derivatives also have much lower lumi-
d6 were taken before and after irradiation of the sample with a
nescent efficiencies and, concomitantly, shorter emission decay
handheld UV lamp. Nearly complete conversion (>95%) to the
lifetimes than their facial counterparts. Assuming that the
corresponding facial isomers was found to occur after less than
emitting state of a complex is formed with unit efficiency, one
2 h of irradiation. This photochemical mer-to-fac conversion
can calculate the radiative (kr) and nonradiative (knr) rate
was observed for all of the Ir(C∧N)3 complexes reported here.
constants using the relationships kr ) ΦPL/τ and ΦPL )
The photoisomerization process is slower in less-coordinating
kr/(kr + knr). The calculated radiative and nonradiative rate
solvents; thus, a sample of mer-Ir(tpy)3 in toluene-d8 took 72 h
constants for the phenylpyridyl-based complexes are listed in
to undergo a similar degree of conversion to the fac-isomer.
Table 5. The fac- and mer-isomers have similar radiative rate
No intermediate species were observed when the NMR spectrum
constants; however, the nonradiative rate constants for the mer-
of this sample was examined at various time intervals during
isomers are more than an order of magnitude larger than those
the photolysis (see Supporting Information). A clean mer-to-
of the fac-isomers. The nonradiative rate constant is a sum of
fac isomerization process is also indicated from the observation
rates for several processes that quench emission. One of these
of isobestic points in the absorption spectra of mer-Ir(tpy)3, taken
(42) Murov, S. L.; Carmichael, I.; Hug, G. L. Handbook of Photochemistry;
at various stages of the photolysis in 2-methyltetrahydrofuran
Marcel Dekker, Inc.: New York, 1993. (see Supporting Information).
7386 J. AM. CHEM. SOC. 9 VOL. 125, NO. 24, 2003
Tris-cyclometalated Iridium(III) Complexes ARTICLES

The greater thermodynamic stability of the fac-Ir(C∧N)3 meridional excited state, acting as an effective quenching
complexes relative to the mer-isomers can be contrasted to the pathway and giving subsequent isomerization to the facial form.
greater stability of mer-Ru(btpz)3 [btpz ) 1-(2′-(4′,5′-benzothia- The photochemical isomerization of meridional Ir(C∧N)3
zolyl)pyrazolyl)]19 and mer-Al(8-hydroxyquinolyl)343 relative to complexes provides a new route to prepare the facial isomers,
their respective facial analogues. This has been attributed to at temperatures much lower than conditions previously em-
the relief of steric interactions in the latter mer-compounds. The ployed to make these complexes. This synthetic procedure can
differing stability between fac- and mer-isomers of N∧N and then lead to more efficient utilization of the iridium precursor
C∧N tris-chelates may be brought about by the preference for materials because high reaction temperatures can promote
maintaining the three strong trans influence phenyl groups of undesired side reactions, decreasing product yields. Also, many
the cyclometalates on the same face of the molecule, trans to potentially interesting and useful cyclometalating ligands have
the heterocyclic groups. The thermodynamic instability of the substituents that are unstable in the harsh reaction conditions
meridional configuration is supported by the DFT calculations required by the prior synthetic methods. Therefore, a greater
which show a ∼30 kJ/mol stabilization of total energy in favor variety of compounds can now be considered as potential ligands
of the fac-isomers. for facial tris-cyclometalated iridium complexes. In addition to
Conclusion the synthetic utility of these reactions, the mechanisms of the
thermal and photochemical mer-to-fac isomerizations are of
The preparative methods for tris-cyclometalates reported here interest. Investigations into the mechanisms of these isomer-
demonstrate that controlling the reaction conditions can impart ization processes are currently being pursued in our laboratories.
significant control in the product configuration. For all of the
cyclometalating ligands studied here, there is a preference to Acknowledgment. The authors thank Universal Display Corp.
form the facial isomers at high temperatures (>200 °C) and and the Defense Advanced Research Projects Agency for
the meridional isomers at lower temperatures (<150 °C). At financial support of this work.
high temperatures, the meridional isomer can be efficiently
converted to the facial form, demonstrating the facial isomer is Supporting Information Available: 1H NMR spectra, 1H and
13C NMR chemical shifts and coupling constants, UV-vis
the thermodynamic product and the meridional form is the
kinetic product. The differences in the ligand configuration of absorption and emission spectra, and table of DFT-calculated
these complexes result in significantly different electrochemical orbital energies for all of the facial and meridional Ir(C∧N)3
and photophysical properties. The meridional isomers are easier compounds examined here, as well as HOMO and LUMO plots
to oxidize, and the emission is broad and red-shifted relative to for fac- and mer-isomers of Ir(ppz)3 and a series of absorption
the facial forms. The solution photoluminescent quantum and 1H NMR spectra showing the photoconversion of mer-Ir-
efficiencies of the meridional isomers and their emission (tpy)3 to fac-Ir(tpy)3 (PDF). Also included are tables of crystal
lifetimes are significantly lower than the facial isomers of the data, atomic coordinates, bond distances, bond angles, and
same cyclometalating ligands. The large difference between the anisotropic displacement parameters for mer-Ir(tpy)3, fac- and
quantum efficiencies of the meridional and facial isomers can mer-isomers of Ir(ppz)3, and fac- and mer-isomers of Ir(tfmppz)3,
be explained by an efficient bond breaking process for the as well as the corresponding CIF files. This material is available
free of charge via the Internet at http://pubs.acs.org.
(43) Utz, M.; Chen, C.; Morton, M.; Papadimitrakopoulos, F. J. Am. Chem.
Soc. 2003, 125, 1371. JA034537Z

J. AM. CHEM. SOC. 9 VOL. 125, NO. 24, 2003 7387