Electrochemically mediated atom transfer radical polymerization triggered by alternating current Francesco De Bon 1 , Vanessa Pereira 1 , Marco Fantin 2 , Armenio C. Serra 1 , Krzysztof Matyjaszewski 3 , Jorge F.J. Coelho 1 1 University of Coimbra, Portugal, 2 Department of Chemical Sciences, University of Padova, Italy, 3 Department of Chemistry, Carnegie Mellon University, USA Electrolysis utilizing alternating current (AC) has often been perceived as a niche approach in the realm of electrosynthesis, overshadowed by continuous or pulsed direct current (DC) electrolysis. However, its potential in driving the regeneration of CuI, in electrochemically mediated Atom Transfer Radical Polymerization (eATRP), is of significant interest. Until now, continuous, or pulsed DC electrolysis stood as the primary means for CuI regeneration in eATRP.1 The rapid change of electrode polarity inherent in AC electrolysis hindered the utilization of mixed metal electrode couples, which can lead to ineffectiveness in the regeneration process for certain metals or alloys. Yet, with the use of Cu0 electrodes, the distinction between anode and cathode vanishes when the electrode’s polarity is altered. Moreover, Cu0 has dual functionality as a supplemental activator and a reducing agent (SARA ATRP) by activating alkyl halides and regenerating the CuI activator through a comproportionation reaction, respectively. Here, we introduce AC electrolysis with real sinusoidal, triangular, and squarewave waveforms at low frequency. Leveraging some of the most active ATRP catalysts known to date, we demonstrate the suitability of these waveforms to produce controlled polymers with Ð as low as 1.03. These findings show that AC electrolysis in eATRP offers an unexpected versatile and efficient approach for macromolecular synthesis. References 1. De Bon F., Lorandi F., Coelho J.F.J., Serra A.C., Matyjaszewski K., Isse AA. Dual electrochemical and chemical control in atom transfer radical polymerization with copper electrodes. Chem Sci 2022, 13(20): 6008-6018. 2. F.D.B. thanks FCT − Fundaça̧ o para a Ciencia e a Tecnologia (Portuguese Foundation for Science and Technology) 3. for financial support through the grants POLYELECTRON (PTDC/EQU-EQU/2686/2020),UIDB/00285/2020 and LA/P/0012/2020.
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© The Author(s), 2023
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