Electron and Proton Transfer Mechanisms From Marcus to Supramolecular Constructions

Abstract

Since the middle of the last century, special attention has been devoted to the study of phenomenological and theoretical aspects of the elementary act of electron and/or proton transfer. The initially proposed model, based on the Frank-Condon principle, suffered from a violation of the law of energy conservation, until R.A. Marcus assumed that energy levels can be adjusted via fluctuations in the polar environment. This model had hard limitations on multielectron transfers. A little later H. Taube drew attention that the model of “solid balls” refers only to a small class of reactions. An important class of compounds with unusual reactivity and the possibility of synchronous multi-electron transfers turned out to be complexes with partial charge transfer. Now one can see the notable interest and, accordingly, a significant number of publications relate to multielectronic (up to 8 electrons!) synchronous transfers in organized nanostructured systems used in electrochemical energy storage devices with high energy density.