Photochemistry of tetraalkylammonium tetrachlorocuprates in low-temperature matrices

Abstract

The product composition and the principles of photochemical transformations of tetrahexylammo- nium 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.