LAUSR

We report a new series of homoleptic Ni(I) bis-N-heterocyclic carbene complexes with a range of torsion angles between the two ligands from 68° to 90°. Electron paramagnetic resonance measurements revealed a strongly anisotropic g-tensor in all complexes with a small variation in g∥ ∼ 5.7-5.9 and g⊥ ∼ 0.6. The energy of the first excited state identified by variable-field far-infrared magnetic spectroscopy and SOC-CASSCF/NEVPT2 calculations is in the range 270-650 cm-1. Magnetic relaxation measured by alternating current susceptibility up to 10 K is dominated by Raman and direct processes. Ab initio ligand-field analysis reveals that a torsion angle of <90° causes the splitting between doubly occupied dxz and dyz orbitals, which has little effect on the magnetic properties, while the temperature dependence of the magnetic relaxation appears to have no correlation with the torsion angle.