Abstract
The reductive and oxidative fluorescence quenching of the 3-substituted phenanthrenes (XH, CN, Cl, Br, CH 3, (CH 3) 2CH, CH 3O) by amines, dimethyl fumarate and fumaronitrile were studied. Fluorescent exciplexes are observed for dimethyl fumarate and fumaronitrile systems in benzene at room temperature. The maximum fluorescence energies can be correlated with Rehm and Weller theoretical calculations. The systematic shifts in exciplex energies also correlate linearly with the Hammett σ p constants. Linear correlations are also observed between the quenching constants k q and the Hammett σ p constants for amine quenching. A simple frontier molecular orbital theory is proposed for the linear correlation of exciplex fluorescence. The effect of the substituent on the lifetime of the exciplexes was also investigated.
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