Synthesis and Characterization of Facial and Meridional Tris-cyclometalated Iridium(III) Complexes

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 → 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.