Chemical Physics Letters, Vol.659, 234-236, 2016
Unexpected effect of substituents on the zero-field splitting of triplet phenyl nitrenes
The EPR spectrum of triplet 2,4,6-tribromophenyl nitrene was obtained in glassy methylcyclohexane at 15 K. Surprisingly, the zero-field splitting parameter D = 0.989 cm(-1) derived from this spectrum is much lower than that reported previously for triplet 3,5-diazido-2,4,6-tribromophenyl nitrene and has the same value as in phenyl nitrenes composed with light atoms. DFT calculations of the zero-field splitting parameters support this unexpected experimental observation. Experimental and theoretical data provide evidence that the enhanced by bromine atoms spin-orbit contribution to the parameter D (the so called "heavy-atom effect") is strongly modulated by other substituents attached to the aromatic cycle. (C) 2016 Elsevier B.V. All rights reserved.