Photochemistry of tetraalkylammonium tetrachlorocuprates in low-temperature matrices

The product composition and the principles of photochemical transformations of tetrahexylammonium tetrachlorocuprate [(RH)4N+]2[CuIICl4]2− (RH = C6H13) in 2-chlorobutane at 77 K have been found out by ESR spectroscopy. It has been shown that the photolysis of [(RH)4N+]2 [CuIICl4]2− results in the formation of alkyl radicals (R⊙), presumably, anions [CuICl3]2− and organic copper(II) compounds {CuIIR}. 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 [CuIICl4]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.