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Comparisons of Photo‐Fries Rearrangements of 4‐Dodecylphenyl Phenylacetate and Two Structurally Related Esters in Hexane and Polyethylene Cages. How Important Are Anchoring Chains? †
Author(s) -
Luo Chuping,
Passin Philippe,
Weiss Richard G.
Publication year - 2006
Publication title -
photochemistry and photobiology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.818
H-Index - 131
eISSN - 1751-1097
pISSN - 0031-8655
DOI - 10.1562/2005-05-26-ra-546
Subject(s) - chemistry , phenylacetate , alkyl , fries rearrangement , polyethylene , hexane , singlet state , reactivity (psychology) , selectivity , crystallinity , side chain , photochemistry , organic chemistry , polymer chemistry , polymer , crystallography , catalysis , medicine , biochemistry , physics , alternative medicine , pathology , nuclear physics , excited state
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.