Matrix isolation and magnetic parameters of septet 3,5-dicyanopyridyl-2,4,6-trinitrene

摘要

Septet 3,5-dicyanopyridyl-2,4,6-trinitrene was synthesized together with quintet 2-azido-3,5-dicyanopyridyl-4,6-dini-trene, quintet 4-azido-3,5-dicyanopyridyl-2,6-dinitrene, triplet 2,6-diazido-3,5-dicyanopyridyl-4-nitrene, and triplet 2,4-diazido-3,5-dicyanopyridyl-6-nitrene by photolysis of 2,4,6-triazido-3,5-dicyanopyridine in solid argon at 4 K. Theelectronic and magnetic properties of the matrix-isolated nitrenes were studied using electron paramagnetic resonance(EPR) spectroscopy in combination with density functional theory (DFT) calculations. The fine-structure parameters of thenitrenes were determined with high accuracy from spectral simulations. All signals in the EPR spectra of the nitrenes,randomly oriented in the solid phase, were unambiguously assigned based on eigenfield calculations of the Zeemanenergy levels and angular dependences of resonance fields.