Bingqing Liu, Svetlana Kilina, Huimin Yin, Peng Cui, Marc Hetu, Susan Monro, Anderson Fuller, Sherri A. McFarland, Wei Xu, Wenfang Sun, Li Wang, and Colin G. Cameron
A series of cationic heteroleptic iridium(III) complexes bearing tris-diimine ligands [Ir(phen)2(R-phen)]3+ (R-phen = phenanthroline (1), 3,8-diphenylphenanthroline (2), 3,8-dipyrenylphenanthroline (3), 3-phenylphenanthroline (4), 3-pyrenylphenanthroline (5), and 3,8-diphenylethynylphenanthroline (6)) were synthesized and characterized. These complexes possessed phen ligand-localized 1π,π* transitions below 300 nm, and charge transfer (1CT) and/or 1π,π* transitions between 300 and 520 nm. In 1, 2, 4, and 6, the low-energy bands were mixed 1CT/1π,π*. However, the increased π-donating ability of the pyrenyl substituent(s) in 3 and 5 split the low-energy bands into a pyrene-based 1π,π* transition at 300–380 nm and an intraligand charge transfer (1ILCT) transition at 380–520 nm. All complexes were emissive at room temperature in CH3CN, but the parentage of the emitting state varied depending on the R substituent(s). Complex 1 exhibited predominantly phen ligand-localized 3π,π* emission mixed with metal-to-lig...