Proton-Coupled Electron Transfer in a Ruthenium(II) Bipyrimidine Complex in Its Ground and Excited Electronic States

Proton-coupled electron transfer (PCET) was studied for the ground and excited electronic states of a [Ru(terpy)(bpm)(OH₂)(PF₆)₂] complex, Ru-bpm. Cyclic voltammetry measurements show that the Ru(II)-aqua moiety undergoes PCET to form a Ru(IV)-oxo moiety in the anodic region, while the bpm ligand undergoes PCET to form bpmH₂ in the cathodic region. The photophysical behavior of Ru-bpm was studied using steady-state and femtosecond transient UV-vis absorption spectroscopy, coupled with density functional theory (DFT) calculations. The lowest-lying excited state of Ru-bpm is described as a (Ru → bpm) metal-to-ligand charge-transfer (MLCT) state, while the metal-centered (MC) excited state was found computationally to be close in energy to the lowest-energy bright MLCT state (MC state was 0.16 eV above the MLCT state). The excited-state kinetics of Ru-bpm were found via transient absorption spectroscopy to be short-lived and were fit well to a biexponential function with lifetimes τ₁ = 4 ps and τ₂ = 65 ps in aqueous solution. Kinetic isotope effects of 1.75 (τ₁) and 1.61 (τ₂) were observed for both decay components, indicating that the solvent plays an important role in the excited-state dynamics of Ru-bpm. Based on the pH-dependent studies and the results from prior studies of similar Ru-complexes, we hypothesize that the ³MLCT state forms an excited-state hydrogen-bond adduct with the solvent molecules and that this process occurs with a 4 ps lifetime. The formation of such a hydrogen-bond complex is consistent with the electronic density accumulation at the peripheral N atoms of the bpm moiety in the ³MLCT state. The hydrogen-bonded state ³MLCT decays to the ground state with a 65 ps lifetime. Such a short lifetime is likely associated with the efficient vibrational energy transfer from the ³MLCT state to the solvent.