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Updated: Oct 7, 2025

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Published on: April 14, 2020
Extreme g-Tensor Anisotropy and Its Insensitivity to Structural Distortions in a Family of Linear Two-Coordinate
William J M Blackaby1, Katie L M Harriman2, Samuel M Greer3,4
1Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
Abstract:
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 d and d 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.
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