Highly Phosphorescent Iridium Complexes Containing Both Tridentate Bis(benzimidazolyl)-benzene or -pyridine and Bidentate Phenylpyridine:  Synthesis, Photophysical Properties, and Theoretical Study of Ir-Bis(benzimidazolyl)benzene Complex

Novel mixed-ligand Ir(III) complexes, [Ir(L)(N∧C)X]<i><sup>n</sup></i><sup>+</sup> (L = N∧C∧N or N∧N∧N; X = Cl, Br, I, CN, CH<sub>3</sub>CN, or −CCPh; <i>n</i> = 0 or 1), were synthesized, where N∧C∧N = bis(<i>N</i>-methylbenzimidazolyl)benzene (Mebib) and bis(<i>N</i>-phenylbenzimidazolyl)benzene (Phbib), N∧N∧N = bis(<i>N</i>-methylbenzimidazolyl)pyridine (Mebip), and N∧C = phenylpyridine (ppy) derivatives. The X-ray crystal structures of [Ir(Phbib)(ppy)Cl] and [Ir(Mebib)(mppy)Cl] [mppy = 5-methyl-2-(2‘-pyridyl)phenyl] indicate that the nitrogen atom of the ppy ligand is located trans to the coordinating carbon atom in Me- or Phbib, while the coordinating carbon atom in ppy occupies the trans position of Cl. [Ir(Mebip)(ppy)Cl]<sup>+</sup> showed a quasireversible Ir(III/IV) oxidation wave at +1.05 V, while the Ir complexes, [Ir(Mebib)(ppy)Cl], were oxidized at +0.42 V versus Fc/Fc<sup>+</sup>. The introduction of an Ir−C bond in [Ir(Mebib)(ppy)Cl] induces a large potential shift of 0.63 V in a negative direction. Further, the oxidation potential of [Ir(Mebib)(Rppy)X] was altered by the substitution of R, R‘, and X groups. Compared to the oxidation potential, the first reduction potential revealed an almost constant value at −2.36 to −2.46 V for [Ir(L)(ppy)Cl] (L = Mebib and Phbib) and −1.52 V for [Ir(Mebip)(ppy)Cl. The UV−vis spectra of [Ir(Mebib)(R-ppy)X] show a clear singlet metal-to-ligand charge-transfer transition around 407∼425 nm and a triplet metal-to-ligand charge-transfer transition at 498∼523 nm. [Ir(Mebip)(ppy)Cl]<sup>+</sup> emits at 610 nm with a luminescent quantum yield of Φ = 0.16 at room temperature. The phosphorescence of [Ir(Mebib)(ppy)X] was observed at 526 nm for X = CN and 555 nm for X = Cl with the high luminescent quantum yields, Φ = 0.77∼0.86, at room temperature. [Ir(Phbib)(ppy)Cl] shows the emission at 559 nm with a luminescent quantum yield of Φ = 0.95, which is an unprecedentedly high value compared to those of other emissive metal complexes. Compared to the luminescent quantum yields of the Ir(ppy)<sub>2</sub>(L) derivatives and [Ir(Mebip)(ppy)Cl]<sup>+</sup>, the neutral Ir complexes, [Ir(L)(R-ppy)X] (L = Me- or Phbib), reveal very high quantum yields and large radiative rate constants (<i>k</i><sub>r</sub>) ranging from 3.4 × 10<sup>5</sup> to 5.5 × 10<sup>5</sup> s<sup>-1</sup>. The density functional theory calculation suggests that these Ir complexes possess dominantly metal-to-ligand charge-transfer and halide-to-ligand charge-transfer excited states. The mechanism for a high phosphorescence yield in [Ir(bib)(ppy)X] is discussed herein from the perspective of the theoretical consideration of radiative rate constants using perturbation theory and a one-center spin−orbit coupling approximation.