Abstract
The dependence of exciplex emission spectra on the solvent polarity was studied for exciplexes with the Gibbs free energy of excited-state electron transfer, ΔG*et, exceeding –0.1 eV (for pyrene, fluoranthene, 1,12-benzoperylene, and 9-cyanoanthracene with methoxybenzenes or dimethylnaphthalene). These exciplexes showed stronger changes in the spectral shift of exciplex emission and the extent of charge transfer with increasing solvent polarity than the exciplexes having more negative ΔG*etvalues. The parameters (difference in energy of charge transfer (CT) and locally excited (LE) states in a vacuum, (H022– H011), and the matrix element for electronic coupling of CT and LE states H12and mrelated to the dipole moment of the CT state and the size of the exciplex) determining the extent of charge transfer, the spectral shift, and other properties of exciplexes were evaluated. The parameters H12and mfor the exciplexes examined fall in the interval 0.1–0.5 and 1.0–1.7 eV, respectively, and the difference (H022– H011) is proportional to ΔG*et.
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