A correlation of anodic peak potentials with HOMO energies of various monomers

Electroinitiated cationic polymerization of olefins can be initiated by direct electron transfer from the highest occupied molecular orbital (HOMO) of monomers, by constant potential electrolysis. Potentials, at which some monomers lose electrons, were measured by cyclic voltammetry. Measurements were made on a Pt electrode versus Ag0/Ag+, in acetonitrile. The measured anodic peak potentials (Ep,a) were correlated to HOMO energies (ϵm), calculated by Hückel molecular orbital (HMO) considerations for coplanar molecules. For methyl‐substituted monomers the ω‐technique was also applied. A linear equation has been developed for Ep,a as a function of ϵm, for styrene derivatives having +I and +E substituents.