High Intrinsic Phosphorescence Efficiency and Density Functional Theory Modeling of Ru(II)-Bipyridine Complexes with π-Aromatic-Rich Cyclometalated Ligands: Attributions of Spin–Orbit Coupling Perturbation and Efficient Configurational Mixing of Singlet Excited States

A series of π-aromatic-rich cyclometalated ruthenium(II)-(2,2'-bipyridine) complexes ([Ru(bpy)₂(π_Ar-CM)]⁺) in which π_Ar-CM is diphenylpyrazine or 1-phenylisoquinoline were prepared. The [Ru(bpy)₂(π_Ar-CM)]⁺ complexes had remarkably high phosphorescence rate constants, k _RAD(p), and the intrinsic phosphorescence efficiencies (ι_em(p) = k _RAD(p)/(ν_em(p))³) of these complexes were found to be twice the magnitudes of simply constructed cyclometalated ruthenium(II) complexes ([Ru(bpy)₂(sc-CM)]⁺), where ν_em(p) is the phosphorescence frequency and sc-CM is 2-phenylpyridine, benzo[h]quinoline, or 2-phenylpyrimidine. Density functional theory (DFT) modeling of the [Ru(bpy)₂(CM)]⁺ complexes indicated numerous singlet metal-to-ligand charge transfers for ¹MLCT-(Ru-bpy) and ¹MLCT-(Ru-CM), excited states in the low-energy absorption band and ¹ππ*-(aromatic ligand) (¹ππ*-L_Ar) excited states in the high-energy band. DFT modeling of these complexes also indicated phosphorescence-emitting state (T_e) configurations with primary MLCT-(Ru-bpy) characteristics. The variation in ι_em(p) for the spin-forbidden T_e (³MLCT-(Ru-bpy)) excited state of the complex system that was examined in this study can be understood through the spin-orbit coupling (SOC)-mediated sum of intensity stealing (∑SOCM-IS) contribution from the primary intensity of the low-energy ¹MLCT states and second-order intensity perturbation from the significant configuration between the low-energy ¹MLCT and high-energy intense ¹ππ*-L_Ar states. In addition, the observation of unusually high ι_em(p) magnitudes for these [Ru(bpy)₂(π_Ar-CM)]⁺ complexes can be attributed to the values for both intensity factors in the ∑SOCM-IS formalism being individually greater than those for [Ru(bpy)₂(sc-CM)]⁺ ions.