Fusion Position-Dependent Aromatic Transitions of Ligand Backbone Rings for Controlling the Redox Energetics of Photoredox Catalysts.

ABSTRACT

To reveal, quantify, and rationalize the effect of backbone π-extension on ligand redox activity, we studied the ground- and excited-state reduction potentials of eight ruthenium photoredox catalysts with the formula Ru(ppy)2L (L is the redox-active ligand of the bipyridine family) using density functional theory. Our research underlines the profound importance of the fusion position of backbone aromatic C6 rings on the redox activity of ligands in transition metal photoredox catalysts. Namely, certain fusion positions lead to the dearomatization of C6 rings in ligand-centered electron transfer events, resulting in a thermodynamic penalty equivalent to a half-volt negative shift in the reduction potential. Contrarily, the extent of backbone delocalization shows a minimal impact on redox energetics, which can be explained by the charge concentration at the nitrogen contact atoms in ligand-centered reductions. Grounded in Caulton's conceptual framework, we reaffirm the predictive potency of Lewis structures in ligand-centered redox energetics with qualitative and quantitative data. Our hypothesis regarding the effect of backbone ring dearomatization on redox energetics is further corroborated using magnetic and structure-based aromaticity indicators. Highlighting fusion-dependent dearomatization as a determining factor of ligand-centered electron transfer energetics, our findings hold implications for molecular-level design in advanced electroactive materials and catalysts.