Abstract
Rate constants kq of the fluorescence quenching of 9,10-dicyanoanthracene by bromide and chloride ions and of 9-cyanoanthracene by bromide ions were determined in the low polar solvent dichloromethane with a series of tetra-alkylammonium counterions. Cation size dependent electron transfer rate constants ket were derived from kq, and were fitted to a nonadiabatic electron transfer model equation. Because of ion pair formation in dichloromethane electrostatic interactions of the redoxinert countercations during electron transfer were considered. Accordingly, the position of the countercation within the precursor complex had to be described.The electronic coupling matrix element derived by fitting of the experimental data is in satisfactory agreement with results of simple quantum chemical calculations.
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Schedule a callMore From: Journal of Photochemistry & Photobiology, A: Chemistry
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