Electro-Photoredox Catalysis under Red Light: From Challenging C-X Bond Cleavage to Controlled Radical Polymerizations under Mild Conditions

Visible light photocatalysis is a well-established tool for driving selective and sustainable processes in the fields of organic synthesis and polymer science. Nevertheless, its widespread adoption is often hampered by short excited-state lifetimes and narrow potential windows of traditional photocatalysts. Electrochemically mediated photoredox catalysis (ePRC) overcomes these limitations by merging traditional electrosynthesis with photoredox catalysis, effectively combining the power of electricity and light within the same catalytic cycle. This thesis leverages the synergistic interplay between electrons and red or near-infrared photons to address (i) the understanding of the electron-transfer mechanism involved in the activation of recalcitrant C–X bonds, and (ii) the development of well-defined polymeric materials under mild conditions via RAFT polymerization. By bridging fundamental mechanistic studies – including the role of solvated electrons – with synthetic utility, this work establishes ePRC as a versatile and energy-efficient platform that spans from advanced organic synthesis at extreme redox potentials to low-energy spatiotemporal control of polymerization kinetics.