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.
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