Selectivity in photolysis of benzyl acetate and benzyl hexanoate upon cyclodextrin complexation

Irradiation of benzyl acetate (1) and benzyl hexanoate (2) in methanol yields products from both heterolytic and homolytic pathways. However, in presence of cyclodextrin, photolysis of 1 in aqueous solution and in solid state produces benzyl alcohol as the predominant product and this is attributed to the stabilization of benzylcarbonium ion by secondary hydroxyl groups present at the rim of the cyclodextrin cavity. However, photolysis of 2, in presence of cyclodextrin, produces hexylbenzene as the predominant product via a homolytic pathway and the change in selectivity is explained by the coinclusion of spacer group inside the cyclodextrin cavity.