Electrochemically Mediated Atom Transfer Radical Polymerization Driven by Alternating Current

Abstract Alternating current (AC) and pulsed electrolysis are gaining traction in electro(organic) synthesis due to their advantageous characteristics. We employed AC electrolysis in electrochemically mediated Atom Transfer Radical Polymerization ( e ATRP) to facilitate the regeneration of the activator Cu I complex on Cu 0 electrodes. Additionally, Cu 0 served as a slow supplemental activator and reducing agent (SARA ATRP), enabling the activation of alkyl halides and the regeneration of the Cu I activator through a comproportionation reaction. We harnessed the distinct properties of Cu 0 dual regeneration, both chemical and electrochemical, by employing sinusoidal, triangular, and square‐wave AC electrolysis alongside some of the most active ATRP catalysts available. Compared to linear waveform (DC electrolysis) or SARA ATRP (without electrolysis), pulsed and AC electrolysis facilitated slightly faster and more controlled polymerizations of acrylates. The same AC electrolysis conditions could successfully polymerize eleven different monomers across different mediums, from water to bulk. Moreover, it proved effective across a spectrum of catalyst activity, from low‐activity Cu/2,2‐bipyridine to highly active Cu complexes with substituted tripodal amine ligands. Chain extension experiments confirmed the high chain‐end fidelity of the produced polymers, yielding functional and high molecular‐weight block copolymers. SEM analysis indicated the robustness of the Cu 0 electrodes, sustaining at least 15 consecutive polymerizations.