Abstract

In this study a detailed scrutiny of the electronic structure changes during the redox events of the oxidative and reductive quenching cycles of the representative homoleptic and heteroleptic octahedral iridium [Ir(bpy)x(ppy)3-x]x+ (x = 0, 1, 2, and 3) and ruthenium [Ru(bpy)x(ppy)3-x]x-1+ (x = 1, 2, and 3) photoredox catalysts is provided through the corresponding electron density difference Δρ(r) distributions. The systematic analysis of the Δρ(r) distributions provides intuitive insights into the details of the metal- and ligand-centered electron transfer processes that take place in the different excited- and ground-state redox steps of classical photoredox catalysis. In addition to the structural metrics, the measured ground-state reduction potentials were also reproduced with great accuracy, typically within 0.15 V, when using the TPSSh functional in combination with the Def2-TZVP basis set coupled to reparameterized implicit solvation model (SMD). We computed the excited-state reduction potentials of these ruthenium and iridium complexes without using TD-DFT, but by directly computing the solution-state Gibbs free energy of the triplet 3MLCT state, giving good agreement with respective experiments. The analyzed Δρ(r) maps reveal the characteristic features of metal- and ligand-centered reductions and oxidations in both ground- and excited states and metal-to-ligand charge transfers (MLCT), sometimes perturbed by additional ligand-to-ligand charge transfer (LLCT) contributions. One of the most interesting features of ligand-centered redox processes is the localization of the accumulated electron density at one redox-active ligand in the case of heteroleptic systems [Ir(bpy)(ppy)2]+ and [Ru(bpy)(ppy)2]0, which is in contrast to the delocalized nature of the ligands-hosted charge in homoleptic photoredox catalysts, such as the classical [Ru(bpy)3]2+ system.