On the Importance of Ligand-Centered Excited States in the Emission of Cyclometalated Ir(III) Complexes

[Image: see text] The photophysical behavior of the cyclometalating Ir(III) complexes [Ir(ppy)(2)(bpy)](+), where Hppy is 2-phenylpyridine and bpy is 2,2′-bipyridine (complex 1), and [Ir(diFppy)(2)(dtb-bpy)](+), where diFppy is 2-(2,4-difluorophenyl)pyridine and dtb-bpy is 4,4′-di-tert-butyl-2,2′-bipyridine (complex 2), has been theoretically investigated by performing density functional theory calculations. The two complexes share the same molecular skeleton, complex 2 being derived from complex 1 through the addition of fluoro and tert-butyl substituents, but present notable differences in their photophysical properties. The remarkable difference in their emission quantum yields (0.196 for complex 1 in dichloromethane and 0.71 for complex 2 in acetonitrile) has been evaluated by characterizing both radiative and nonradiative decay paths. It has emerged that the probability of decaying through the nonradiative triplet metal-centered state, normally associated with the loss of the emission quantum yield, does not appear to be the reason behind the reported substantially different emission efficiency. A more critical factor appears to be the ability of complex 2 to emit from both the usual metal-to-ligand charge-transfer state and from two additional ligand-centered states, as supported by the fact that the respective minima belong to the potential energy surface of the lowest triplet T(1) state and that their phosphorescence lifetimes are in the same order of magnitude. In contrast, the emission of complex 1 can be originated only from the metal-to-ligand charge-transfer state, being the only emissive T(1) minimum. The results constitute a significant case in which the emission from ligand-centered states is the key for determining the high emission quantum yield of a complex.