A correlation between the rates of photoinduced long-range intramolecular electron transfer in rigidly linked donor-acceptor systems and computed π,π and π *,π * splitting energies in structurally related dienes

Abstract

It has been found that the rates of photoinduced intramolecular electron transfer in a series of rigidly linked donor (dimethoxynaphthalene)-acceptor (dicyanovinyl) systems, in which the length and configuration of the hydrocarbon bridge are varied, correlate well with the computed Koopmans' theorem STO-3G π *,π * splitting energies in a structurally related series of dienes. It is proposed that the origin of this correlation lies in a through-bond coupling mechanism which obtains between the π * LUMOs of the chromophores and the bridge σ and σ * orbitals in both series of molecules.