The Mechanism of Electrochemically-Mediated Photoredox Catalysis with Organic Superoxidants

The combination of one photon and one electron through the concomitant use of photocatalysis and electrochemistry creates a tool with unprecedented reactivity, capable of driving extremely challenging reactions. The aim of this thesis was to investigate the electrochemical characteristics of aryl amines as photo-redox catalysts, thanks to their ability to absorb photons after electrochemical oxidation, achieving excited-state potentials up to 4.4 V vs SCE. This remarkable reactivity was tested in the oxidation of benzene derivatives. The mechanism of action of these superoxidants was elucidated through quantitative analysis of the reaction rate constants using a combination of cyclic voltammetry and simulation software.