Captivating bimolecular photoredox dynamics of a ligand-to-metal charge transfer complex

Transition metal complexes featuring ligand-to-metal charge transfer (LMCT) excited states have been identified as promising candidates for driving electron transfer processes. To obtain an efficient system based on photo-induced bimolecular electron transfer, it is required that (1) photo-induced charge separation (CS) is faster than charge recombination (CR) of the separated charges, and (2) CR is slower than their spatial separation via cage escape (CE). Here, we investigate this competitive sequence of processes by the photocycle of a rhenium(ii) complex featuring a strongly oxidizing ²LMCT excited state. Intrinsic CS and CR rates were measured up to multimolar concentrations for several electron donors to elucidate both the diffusion-controlled and close-contact regimes over a wide range of thermodynamic driving forces. Ultrafast dynamics (<200 fs) suggest that CS is dominated by a hot electron transfer component competing with ²LMCT vibrational relaxations in the high-concentration/close-contact regime. The intrinsic CS and CR rates related to the relaxed ²LMCT state dominate the dynamics at intermediate concentrations and show concentration-dependence at 3-50 vol% electron donor concentration and concentration-independence at higher concentrations with τ _CS = 0.5 ps and τ _CR = 2 ps, for the prototype donor anisole. The ratio between CS and CR rates was altered systematically by the thermodynamic driving force of electron transfer, utilizing the fact that the processes lie in the Marcus normal and inverted regions, respectively, and with deviations from classical Marcus behavior accounted for by using Marcus-Jortner-Levich theory. Our findings provide unique insight into the complex competition between kinetic factors controlling the fundamental dynamics of the charge-separated pairs inside the solvent cage for photocycles driven by ²LMCT excited states.