Photochemistry of tetraalkylammonium tetrachlorocuprates in low-temperature matrices

• Published in: High energy chemistry 2009-09, Vol.43 (5), p.384-390
• Main Authors: Lobanov, A. V., Golubeva, E. N., Zubanova, E. M., Mel’nikov, M. Ya
• Format: Article
• Language: English
• Subjects: Chemistry; Chemistry and Materials Science; Photochemistry; Physical Chemistry
• ISSN: 0018-1439; 1608-3148
• DOI: 10.1134/S0018143909050099

The product composition and the principles of photochemical transformations of tetrahexylammonium tetrachlorocuprate [(RH) 4 N + ] 2 [Cu II Cl 4 ] 2− (RH = C 6 H 13 ) in 2-chlorobutane at 77 K have been found out by ESR spectroscopy. It has been shown that the photolysis of [(RH) 4 N + ] 2 [Cu II Cl 4 ] 2− results in the formation of alkyl radicals (R ⊙ ), presumably, anions [Cu I Cl 3 ] 2− and organic copper(II) compounds {Cu II R}. A reduction in the quantum yield of primary photolysis products during the reaction, nonequivalence of the quantum yield of the buildup of paramagnetic photolysis products to that of [Cu II Cl 4 ] 2− consumption, and a decrease in the total number of paramagnetic particles in the system during the photolysis have been revealed. A photolysis mechanism involving both photochemical and thermal processes is proposed.