The irreversible nature of the redox events for monomer 1 was corroborated across a range of scan rates between 50 and 1000 mV/s (S24). The irreversibility suggests a fast chemical reaction occurs immediately following oxidation or reduction. In preliminary investigations, applying a positive potential did not generate polymer from the trisulfide monomers, so this mode of initiation was not pursued further. Instead, electrochemical reduction of cyclic trisulfide monomers 1, 3, and 4 was targeted to initiate ring-opening polymerization by way of a putative radical anion intermediate (see polymerization studies and mechanistic discussion below).