Extreme g-Tensor anisotropy and its insensitivity to structural distortions in a family of linear two-coordinate Ni(I) Bis-N-heterocyclic carbene complexes

Blackaby, William J. M., Harriman, Katie L. M., Greer, Samuel M., Folli, Andrea ORCID: https://orcid.org/0000-0001-8913-6606, Hill, Stephen, Krewald, Vera, Mahon, Mary F., Murphy, Damien M. ORCID: https://orcid.org/0000-0002-5941-4879, Murugesu, Muralee, Richards, Emma, Suturina, Elizaveta and Whittlesey, Michael K. 2022. Extreme g-Tensor anisotropy and its insensitivity to structural distortions in a family of linear two-coordinate Ni(I) Bis-N-heterocyclic carbene complexes. Inorganic Chemistry 61 (3) , pp. 1308-1315. 10.1021/acs.inorgchem.1c02413

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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 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.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Publisher:	American Chemical Society
ISSN:	0020-1669
Date of First Compliant Deposit:	2 February 2022
Date of Acceptance:	20 December 2021
Last Modified:	27 Jan 2023 14:31
URI:	https://orca.cardiff.ac.uk/id/eprint/146706

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