Correlation of voltammetric and spectroscopic data obtained from open- and closed-shell aromatic esters and those obtained from AM1 calculations

Abstract

Results from semi-empirical molecular orbital calculations on a series of pyridine and benzene esters and thioic S-esters (closed-shell) and their associated anion radicals (open-shell) using the MOPAC computer program, the AM1 Hamiltonian and the RHF and UHF methods, have been compared with electrochemical and spectroscopic experimental data obtained in acetonitrile solution containing 0.1 M supporting electrolyte (Et4NPF6). The experimental data considered are reversible half-wave potentials obtained by differential pulse voltammetry and/or cyclic voltammetry, hyperfine splitting constants obtained by in situ electrochemical EPR experiments and absorption spectra obtained by in situ electrochemistry-UV–Vis spectroscopy.