Conformational control of photoinduced decarboxylation of simple aryl esters. Enhancement by templating effects in polyethylene films

The photochemistry of phenyl and 1-naphthyl eaters has been investigated in solutions and in polyethylene films. Enhancement of photodecarboxylation a t the expense of the 'normal' photo-Fries processes when the irradiations a re conducted in polyethylene films at subambient temperatures is attributed to a 'templating' effect imposed by the large solute molecules on the poly mer chains that constitute their reaction cavities. Evidence for the confor mation of the eaters that promotes photodecarboxylation comes from quantum chemical calculations, single-crystal X-ray analyses, and additional interp retation of data in the literature. (C) 2001 Elsevier Science B.V. All righ ts reserved.