The calculated values closely matched the experimentally observed reduction potential of trisulfide monomers 1, 3, and 4 (Fig. ). These comparisons provided confidence in the accuracy of the calculations and corroborated the hypothesis that the initial step in the electrochemical reaction is the addition of an electron to the trisulfide monomer (vide infra). For cyclic pentasulfide monomer 2, the electrochemical reduction was more complicated, as mentioned previously. During this process, the pentasulfide was reduced (-1.6 V versus Fc/Fc + ) and converted into cyclic trisulfide monomer 1. H NMR spectroscopy confirmed this electrochemically-initiated ring contraction (S35-S36). Therefore, the peak at -2.2 V versus Fc/Fc + in the cyclic voltammogram of monomer 2 is actually due to reduction of monomer 1 formed during the measurement. Following the cyclic voltammetry measurements, chronoamperometry experiments were then conducted by applying a constant potential of -2 and +2 V versus Ag/AgCl to divided cells containing monomer 1 (S25). Current was observed when a negative potential was applied, and no current was observed when a positive potential was applied. Additionally, a product precipitated in the cathodic chamber in these experiments. This product was later identified as poly-1, providing motivation to investigate and optimize the polymerization of the trisulfide monomers under a reductive potential.