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Title: Evidence of photo- and thermal-induced reversible intermolecular hydrogen-atom transfer in. gamma. -irradiated thiourea clathrates as studied by electron spin resonance

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j100473a023· OSTI ID:6296280

There has been a report (M. Iwasaki and Toriyama) on an electron spin resonance study of reversible intramolecular radical conversion due to photo- and thermal-induced H-atom transfer. Schlenk, Brown, White, Chatini, and Nakatani reported H-atom abstraction of a photostimulated allylic radical from its neighbor molecules and thermal recovery of the allylic radical from photoirradiation in a thiourea clathrate. Radiolysis of a thiourea clathrate containing a mixture of 10 mol% 2,3-dimethylbutadiene and 90 mol% 2,3-dimethylbutane gave a resolved room-temperature spectrum. The result seemed to suggest that the monomer radical was stabilized in the canal even at room temperature in the presence of the inert DBA molecules which might block chain propagation. Results suggested that the photostimulated R/sub 1/, radicals abstract H atoms from DBA molecules to form tetramethylethylene molecules and R/sub 2/ radicals and that the R/sub 2/ radicals produced by photoirradiation abstract H atoms from TME molecules to regenerate R/sub 1/ radicals and DBA molecules. 2 figures. (DP)

Research Organization:
Hiroshima Univ., Japan
OSTI ID:
6296280
Journal Information:
J. Phys. Chem.; (United States), Vol. 83:10
Country of Publication:
United States
Language:
English