Abstract
Oxidative electron-transfer quenching of the lowest ligand-centered /sup 3/..pi pi..* of ruthenium (RU) phthalocyanines (pc)L/sub 2/, L = dimethylformamide (dmf) or pyridine (py), by a series of nitroaromatic compounds, viologen salts, and metal complexes has been investigated by laser and conventional flash photolysis. The quenching rate constants, treated according to Marcus-Hush and Rehm-Weller equations, gave self-exchange rate constants, k/sub exch/ approx. 10/sup 7/ M/sup -1/ s/sup -1/, for the electron exchange between the /sup 3/..pi pi..* and the ruthenium(II) ligand radical. The excited states of a number of phthalocyanines, e.g. Ru(pc)(dimethyl sulfoxide(Me/sub 2/SO)/sub 2/), Ru(pc)(dmf)CO, Ru(pc)(py)CO, and Rh(pc)(methanol(CH/sub 3/OH)chloride), undergo quenching mediated by exciplex formation. The formation of exciplexes is discussed in terms of the related exciplexes of the porphyrins.
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