Abstract
Polarized FT-EPR spectra of photolyzed pyrene/alkali metal (Li, Na, K, Rb, Cs)/THF solutions were found to be time and alkali metal dependent. The polarization effects are initiated by electron transfer (ET) reactions between the doubly- and singly-charged pyrene (Py 2- and Py .- ) and the alkali metal countercations (M + ). With the exception of Py/K/THF solution, the spin polarizations of all other systems, including those with a chelating agent added (cryptand), originate with a triplet precursor. The polarization is due to the action of several mechanisms: the correlated radical pair mechanism, S-T-1 radical pair (RP) mixing, and the radical-triplet pair mechanism
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