Electrochemical Study of Catalytic Cycles that Combine Light Absorption and Electron Transfer: Carbon-Halogen Bond Cleavage via Electrophotocatalysis

Electrophotocatalysis (e-PC) combines electrosynthesis and photoredox catalysis to produce highly reactive species that drive challenging reactions. Despite its promise, the mechanism of e-PC reactions, particularly involving the catalyst naphthalene monoimide (NMI), remains debated, with three distinct mechanisms proposed in recent years. Indeed, to date, no fundamental kinetic and mechanistic studies have been performed on e-PC. This thesis work aims to develop a framework for the investigation of the kinetic and mechanistic aspects of e-PC reactions, mainly using cyclic voltammetry and spectroelectrochemistry. The main focus is on the reaction of carbon-halogen bond cleavage between the radical anion of NMI and organic halides, including recalcitrant C-F and C-Cl bonds.