Low-Temperature Observation of the Excited-State Decay of Ruthenium-(Mono-2,2′:6′,2″-Terpyridine) Ions with Innocent Ligands: DFT Modeling of an ³MLCT-³MC Intersystem Crossing Pathway

The synthesis, electrochemistry, and photophysical characterization of five 2,2′:6′,2″-terpyridine ruthenium complexes (Ru-tpy complexes) is reported. The electrochemical and photophysical behavior varied depending on the ligands, i.e., amine (NH₃), acetonitrile (AN), and bis(pyrazolyl)methane (bpm), for this series of Ru-tpy complexes. The target [Ru(tpy)(AN)₃]²⁺ and [Ru(tpy)(bpm)(AN)]²⁺ complexes were found to have low-emission quantum yields in low-temperature observations. To better understand this phenomenon, density functional theory (DFT) calculations were performed to simulate the singlet ground state (S₀), T_e, and metal-centered excited states (³MC) of these complexes. The calculated energy barriers between T_e and the low-lying ³MC state for [Ru(tpy)(AN)₃]²⁺ and [Ru(tpy)(bpm)(AN)]²⁺ provided clear evidence in support of their emitting state decay behavior. Developing a knowledge of the underlying photophysics of these Ru-tpy complexes will allow new complexes to be designed for use in photophysical and photochemical applications in the future.