Photochemistry of tetraalkylammonium tetrachlorocuprates in low-temperature matrices

The product composition and the principles of photochemical transformations of tetrahexylammonium tetrachlorocuprate [(RH)₄N⁺]₂[Cu^IICl₄]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 [Cu^IICl₄]²⁻ results in the formation of alkyl radicals (R^⊙), presumably, anions [Cu^ICl₃]²⁻ and organic copper(II) compounds {Cu^IIR}. 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^IICl₄]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.