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

William J. M. Blackaby, Katie L. M. Harriman, Samuel M. Greer, Andrea Folli, Stephen Hill, Vera Krewald, Mary F. Mahon, Damien M. Murphy, Muralee Murugesu, Emma Richards, Elizaveta Suturina, Michael K. Whittlesey

Research output: Contribution to journalArticlepeer-review

2 Downloads (Pure)

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.

Original languageEnglish
Pages (from-to)1308-1315
Number of pages8
JournalInorganic Chemistry
Volume61
Issue number3
Early online date10 Jan 2022
DOIs
Publication statusPublished - 24 Jan 2022

Fingerprint

Dive into the research topics of 'Extreme g-tensor anisotropy and its insensitivity to structural distortions in a family of linear two-coordinate Ni(I) bis-N-heterocyclic carbene complexes'. Together they form a unique fingerprint.

Cite this