This work presents a detailed evaluation of the performance of density functional theory (DFT) for the prediction of zero-field splittings (ZFSs) in high-spin nitrenes. A number of well experimentally characterized triplet mononitrenes, quartet nitrenoradicals, quintet dinitrenes, and septet trinitrenes have been considered. Several DFT-based approaches for the prediction of ZFSs have been compared. It is shown that the unrestricted Kohn–Sham and the Pederson–Khanna approaches are the most successful for the estimation of the direct spin-spin (SS) interaction and the spin-orbit coupling (SOC) parts, respectively, to the final ZFS parameters. The most accurate theoretical predictions (within 10%) are achieved by using the PBE density functional in combination with the DZ, EPR-II, and TZV basis sets. For high-spin nitrenes constituted from light atoms, the contribution of the SOC part to ZFS parameters is quite small (7%–12%). By contrast, for chlorine-substituted septet trinitrenes, the contribution of the SOC part is small only to D value but, in the case of E value, it is as large as the SS part and has opposite sign. Due to this partial cancellation of two different contributions, SS and SOC, the resulting values of E in heavy molecules are almost two times smaller than those predicted by analysis of the widely used semiempirical one-center spin-spin interaction model. The decomposition of DSS into n-center (n=1–4) interactions shows that the major contribution to DSS results from the one-center spin-spin interactions. This fact indicates that the semiempirical SS interaction model accurately predicts the ZFS parameters for all types of high-spin nitrenes with total spin S=2 and 3, if their molecules are constructed from the first-row atoms.

The high resolution 9GHz electron paramagnetic resonance (EPR) spectrum of septet pyridyl-2,4,6-trinitrene was recorded after the photolysis of 2,4,6-triazido-3,5-dichloropyridine in solid argon matrix at 15K. Owing to the high resolution of the experimental EPR spectrum, the zero-field splitting parameters of the septet trinitrene were determined with a high accuracy: Ds=−0.1019±0.0004cm−1 and Es=0.00325±0.00015cm−1. All EPR transitions of the septet trinitrene were, for the first, unambiguously assigned based on the eigenfield calculations of the Zeeman energy levels. The spectrum of the septet trinitrene represents a new type of EPR spectra of septet spin states with nonzero zero-field splitting parameter Es. The nonvanishing parameter Es of the septet trinitrene arises due to magnetic nonequivalence of three triplet centers in the molecule and is manifested in the appearance in the spectrum of separate x and y transitions. The septet spin states of this type display at very low magnetic fields two intense z transitions since the ∣3Ds∣ energy gap between zero-field energy levels W±1 and W±2 fits the quantum of microwave irradiation of a 9GHz EPR spectrometer. Analysis of the magnetic parameters shows that semiempirical description of the fine-structure tensor for six electron-spin cluster in the septet trinitrene is appropriate for precise estimations of the parameter Ds but it is too crude to estimate small value of the parameter Es.