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Imidazole. pi. cation and barbital. pi. anion trapped in a cocrystalline complex x-irradiated at 12 K: An ESR--ENDOR study

Journal Article · · J. Chem. Phys.; (United States)
OSTI ID:5011554

The predominant free radicals trapped in single crystals of the 1:1 intermolecular complex of imidazole and 5,5-diethylbarbituric acid (barbital) x-irradiated at 12 K have been identified by ESR and ENDOR. The electron abstraction and electron addition products are found to be the imidazole ..pi.. cation and the barbital ..pi.. anion, respectively. The ..pi.. cation provides experimental evidence of evenly distributed unpaired electron density at positions C/sub 2/, C/sub 4/, and C/sub 5/ of the five membered imidazole ring. In the ..pi.. anion the unpaired electron density is localized primarily on C/sub 4/ of barbital. It is suggested that ..pi.. anions are trapped in barbital in preference to imidazole because barbital has a higher cross section for electron capture than imidazole. On the other hand, ..pi.. cations are trapped in imidazole in preference to barbital because the barbital ..pi.. cation has a higher cross section for destruction than the imidazole ..pi.. cation.

Research Organization:
Department of Radiation Biology and Biophysics, School of Medicine and Dentistry, University of Rochester, Rochester, New York 14642
OSTI ID:
5011554
Journal Information:
J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 73:8; ISSN JCPSA
Country of Publication:
United States
Language:
English