Alkali metal ion controlled product selectivity during photorearrangements of 1-naphthyl phenyl acylates and dibenzyl ketones within zeolites

Abstract

Photochemical behaviors of 1-naphthyl phenyl acylates and dibenzyl ketones included in zeolites have been compared. 1-Naphthyl phenyl acylates while in solution produce eight photoproducts; within NaY it gives a single product. The selectivity is attributed to the restriction brought on the mobility of the primary radical pair by the alkali metal ions present in zeolites. Photochemistry of dibenzyl ketones within NaY reveals that the intersystem crossing in caged radical pairs could be influenced by the heavy alkali metal ions. Structures of complexes among Li+ion and the guest 1-naphthyl phenyl acetates and dibenzyl ketone computed at the B3LYP level have been useful to understand the origin of the observed product selectivity within zeolites.Key words: photo-Fries reaction, zeolites, cation–π interaction, spin-orbit coupling, heavy atom effect.