A CORRELATION BETWEEN THE RATES OF PHOTOINDUCED LONG-RANGE INTRAMOLECULAR ELECTRON-TRANSFER IN RIGIDLY LINKED DONOR-ACCEPTOR SYSTEMS AND COMPUTED PI,PI AND PI-STAR,PI-STAR SPLITTING ENERGIES IN STRUCTURALLY RELATED DIENES

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. © 1990.