Quintet Dinitrenes with Negative Zero-Field Splitting: Effect of Spin-Orbit Coupling on the Sign of Magnetic Anisotropy.

We report on W-band EPR and quantum chemical investigation of novel organic tetraradicals with negative axial zero-field splitting (ZFS) parameter D. These belong to the class of quintet 1,3,5-tribromophenylene-2,4-dinitrenes bearing different substituents in position 6 of the benzene ring (1b, N3; 1c, F; 1d, CN; 1e; Cl; 1f, Br). Analysis of the W-band EPR spectrum of dinitrene 1c reveals its large negative ZFS parameter D = -0.27 cm-1. Quantum chemical calculations show that negative D gradually grows in the row of 1c(F) < 1b(N3) < 1d(CN) < 1e(Cl) < 1f(Br) dinitrenes due to decreasing of the through-space distance between the nitrene units and neighboring bromine atoms. Shorter steric N···Br distance results in the stronger contribution of the spin-orbit coupling (SOC) to the total ZFS. The sign of D depends on the interplay of three factors: (i) the angle θ between the "easy" z-axes of the dipolar spin-spin (DSS) and spin-orbit (DSOC) interaction tensors, (ii) the ratio of DSOC/DSS values, and (iii) the rhombicity parameters ESS/DSS and ESOC/DSOC. The study demonstrates in which cases organic quintet tetraradicals may have negative ZFS owing to the presence of heavy atoms at appropriate sites nearby the nitrene units and, thus, possess the bistability property as single-molecule magnets.