Photochemistry of the Electron Donor-Acceptor System. I. Exciplex Fluorescence and the Fluorescence of the Charge-Transfer Complex in the Aromatic Hydrocarbon–Fumaronitrile System

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The fluorescence of a series of aromatic hydrocarbons was quenched by the addition of fumaronitrile, which is consistent with the charge-transfer or electron-transfer mechanism. The fluorescence quenching was accompanied by the appearance of a new, broad structureless emission band attributed to the fluorescence from the exciplex in non-polar or slightly polar solvents. In highly polar solvents only quenching of the fluorescence occurred. The energies of the band maxima of the exciplex fluorescences and the magnitude of the ionization potentials of a series of fluorescers showed a good correlation with each other. Solvent and temperature dependence of the exciplex fluorescence was examined and discussed. The present aromatic hydrocarbon-fumaronitrile system also formed a charge-transfer complex in their ground states at relatively high concentrations of each component. The selective excitation of the ground state charge-transfer complex gave rise to the fluorescence emission in a fluid solution at room temperature at the same wavelength region as observed for the exciplex fluorescence. It was susgested that the electronic structure of the fluorescent state of the exciplex and the excited charge-transfer complex is the same.
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