Guided by cyclic voltammetry, preliminary computational studies, and the divided cell experiment discussed previously, we arrived at a working hypothesis that a ring-opening reaction of the monomers is induced by cathodic reduction of the monomer. To study this process in greater detail, we targeted the ring-opening polymerization of monomer 4 for its easily identifiable 1 H NMR signals that did not overlap with the electrolyte during analysis of crude reaction mixtures. Monomer 4 (0.04 M) was dissolved in a solution of acetonitrile (15 mL, 0.1 M nBu4NPF6) in an ElectraSyn ® cell containing two glassy carbon electrodes and a Ag/AgCl reference electrode. Glassy carbon was chosen as the working and counter electrode material due to its low cost, wide potential range, and stability under the reaction conditions. While stirring, a constant potential of -2.0 V versus Ag/AgCl was applied to the cell resulting in the immediate formation of precipitate (Fig. ). Over 4 hours the amount of precipitate in the cell increased and became darker in color. The precipitate was collected and purified by successive dissolution in chloroform and precipitation with acetonitrile to isolate the final product for further characterization (S26-S47). The product was soluble in both chloroform and THF, which allowed analysis by 1 H NMR spectroscopy and gel permeation chromatography (GPC), respectively. The 1 H NMR spectrum of the purified product showed broad peaks consistent with a polymer structure (Fig. ). Integration of the alkene signals revealed no reaction occurred at this functional group, which is evidence for chemoselectivity in the ring-opening polymerization.