Controlled Radical Polymerization Enabled by Electrochemically Mediated Photoredox Catalysis.

This thesis explores the convergence of three chemistry branches—electrochemistry, photochemistry, and polymer science—investigating their synergistic interactions at the molecular level to develop novel approaches in controlled polymer synthesis. The research focuses on e-PRC (electrochemically mediated photoredox catalysis), which combines the injection of one electron (or hole) and one photon in a single catalytic cycle, effectively conducting photo-redox catalysis with an excited open shell catalyst in a reduced or oxidized form. Building up on both traditional photo-redox catalysis (PRC) and electrocatalysis (EC), this approach aims to combine the advantages of these two worlds through e-PRC methods to access new possibilities for controlled radical polymerization reactions (CRPs). CRPs allow to obtain polymeric materials with high control over molecular weights (M n ) and their distribution (typically dispersity Đ < 1.5), while minimizing unwanted radical termination reactions and allowing for polymerization to be paused and resumed by removing/applying the external stimuli. Central to this investigation is the use of N,N-bis(2,6-diisopropylphenyl)perylene-3,4,9,10- bis(dicarboximide) (PDI) as a organocatalyst. The photoexcitation of the PDI radical anion (PDI •− ) facilitates reactions using low-energy red light and mild electrochemical potentials, expanding the scope of accessible chemical reactions. A comprehensive investigation into the photochemical and electrochemical properties of PDI evaluates its capacity to generate radicals suitable for new CRPs pathways. This work bridges the fields of photoredox catalysis, electrochemistry, and polymer science, aiming to develop a novel, efficient, and selective CRP method by harnessing the combined power of light and electrons through organocatalysis. Following these steps could potentially lead to more sustainable and energy-efficient polymerization processes, contributing to the broader field of materials science and green chemistry.