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Matrix isolation and magnetic parameters of septet 3,5‐dicyanopyridyl‐2,4,6‐trinitrene
Author(s) -
Chapyshev Sergei V.,
Neuhaus Patrik,
Grote Dirk,
Sander Wolfram
Publication year - 2010
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1622
Subject(s) - nitrene , chemistry , electron paramagnetic resonance , matrix isolation , zeeman effect , density functional theory , photodissociation , matrix (chemical analysis) , resonance (particle physics) , spectroscopy , spectral line , computational chemistry , molecular physics , argon , nuclear magnetic resonance , photochemistry , atomic physics , magnetic field , organic chemistry , physics , quantum mechanics , chromatography , catalysis
Septet 3,5‐dicyanopyridyl‐2,4,6‐trinitrene was synthesized together with quintet 2‐azido‐3,5‐dicyanopyridyl‐4,6‐dinitrene, 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. The electronic 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 the nitrenes 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 Zeeman energy levels and angular dependences of resonance fields. Copyright © 2009 John Wiley & Sons, Ltd.