Comparisons of photo-Fries rearrangements of 4-dodecylphenyl phenylacetate and two structurally related esters in hexane and polyethylene cages. How important are anchoring chains?

Article abstract of DOI:10.1562/2005-05-26-RA-546

Photo-Fries rearrangements of 4-dodecylphenyl phenylacetate have been investigated in polyethylene films with 0-71% crystallinity and in hexane over a range of temperatures. The results are compared to those reported previously from phenyl phenylacetate and 1-naphthyl tetradecanoate to assess the influence of a long alkyl chain on the in-cage motions of the intermediate singlet radical pairs. It is demonstrated that the reactivity and selectivity of intimate singlet radical pairs can be tuned by judicious placement of long-chain substituents and selection of a specific polyethylene type as the reaction matrix.