EPR spectroscopy of multicomponent, multispin molecular system obtained by the photolysis of 2,4,6-triazido-3-cyano-5-fluoropyridine in solid argon.

Abstract

Complex multicomponent, multispin molecular system, consisting of a septet trinitrene, two quintet dinitrenes, and three triplet mononitrenes, was obtained by the photolysis of 2,4,6-triazido-3-cyano-5-fluoropyridine in solid argon. To identify these paramagnetic products, electron paramagnetic resonance spectroscopy in combination with line-shape spectral simulations and density functional theory calculations was used. The products of the photolysis was found to be triplet 2,4-diazido-3-cyano-5-fluoropyridyl-6-nitrene (DT =1.000cm-1 , ET =0), triplet 2,4-diazido-3-cyano-5-fluoropyridyl-2-nitrene (DT =1.043cm-1 , ET =0), triplet 2,6-diazido-3-cyano-5-fluoropyridyl-4-nitrene (DT =1.128cm-1 , ET =0cm-1 ), quintet 4-azido-3-cyano-5-fluoropyridyl-2,6-dinitrene (DQ =0.211cm-1 , EQ =0.0532cm-1 ), quintet 2-azido-3-cyano-5-fluoropyridyl-4,6-dinitrene (DQ =0.208cm-1 , EQ =0.0386cm-1 ), and septet 3-cyano-5-fluoropyridyl-2,4,6-trinitrene (DS =-0.1017cm-1 , ES =-0.0042cm-1 ) in a 38:4:7:22:14:4 ratio, respectively.