TRANSIENT SPECIES IN ELECTRON-TRANSFER - REACTIONS OF CHLORANIL WITH DONOR AROMATIC-COMPOUNDS
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Light-induced intermolecular electron-transfer reactions, particularly the dynamics of the early stages, were studied by means of picosecond absorption spectroscopy. The donor (D)/acceptor (A) systems studied in acetonitrile were naphthalene (NAP)/chloranil (CHL), 9,10-dihydrophenanthrene (DHP)/CHL, and indene (IN)/CHL. Difference absorption spectra taken at selected delay times after excitation of the sample by a 355-nm, 25-ps fwhm laser pulse revealed the sequence of events and the identities of the species involved in the electron-transfer reaction. With this spectroscopic information, we were able to elucidate events which occur in the early stages of the electron-transfer reaction. From the data, we infer that the initially formed ion pair relaxes to an equilibrated cation-anion-solvent complex. 1983, American Chemical Society. All rights reserved.