Selective-Solvation-Induced Intramolecular Electron Transfer: Time Resolution via Pulsed Accelerated Flow Spectrophotometry

Despite extensive theoretical interest, relatively few experimental reports exist concerning nonphotochemical intramolecular electron-transfer (ET) kinetics, at least for chemically reversible (i.e., thermodynamically well-defined) redox systems. Nevertheless, the few that do exist have yielded important insights concerning donor-acceptor electronic coupling and solvent reorganization, especially over longer distances. We wish to report here an experiment which adds in an unusual way to the limited list of both chemical systems and chemical methodologies for inducing intramolecular ET. Our approach is based on the ability of added solvent to influence redox potentials, and therefore oxidation-state distributions, in selected asymmetric mixed-valence systems. 13 refs., 1 fig.