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

doi:10.1021/acs.inorgchem.1c02413

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

Department of Chemistry

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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.

Original language	English
Pages (from-to)	1308-1315
Number of pages	8
Journal	Inorganic Chemistry
Volume	61
Issue number	3
Early online date	10 Jan 2022
DOIs	https://doi.org/10.1021/acs.inorgchem.1c02413
Publication status	Published - 24 Jan 2022

Bibliographical note

Funding Information:
Work performed at the National High Magnetic Field Laboratory is supported by the National Science Foundation (NSF, DMR-1644779) and the State of Florida. Additional support from the NSF (DMR-2004732 to S.H.) is also gratefully acknowledged. S.M.G. acknowledges support from the NSF Graduate Research Fellowship Program (DGE-1449440). Work performed at the University of Ottawa is graciously supported by the University of Ottawa, the Natural Sciences and Engineering Research Council of Canada, and the Canadian Foundation for Innovation. E.S. and M.K.W. thank the University of Bath for HPC facilities for computational time and for a Ph.D. studentship (W.J.M.B.), respectively.

Publisher Copyright:
© 2022 American Chemical Society.

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10.1021/acs.inorgchem.1c02413

Ni bis-NHC Inorg Chem accepted
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.inorgchem.1c02413.
Accepted author manuscript, 9.49 MB

Cite this

Blackaby, W. J. M., Harriman, K. L. M., Greer, S. M., Folli, A., Hill, S., Krewald, V., Mahon, M. F., Murphy, D. M., Murugesu, M., Richards, E., Suturina, E., & Whittlesey, M. 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), 1308-1315. https://doi.org/10.1021/acs.inorgchem.1c02413

Blackaby, WJM, Harriman, KLM, Greer, SM, Folli, A, Hill, S, Krewald, V, Mahon, MF, Murphy, DM, Murugesu, M, Richards, E, Suturina, E & Whittlesey, MK 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, vol. 61, no. 3, pp. 1308-1315. https://doi.org/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.",

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

note = "Funding Information: Work performed at the National High Magnetic Field Laboratory is supported by the National Science Foundation (NSF, DMR-1644779) and the State of Florida. Additional support from the NSF (DMR-2004732 to S.H.) is also gratefully acknowledged. S.M.G. acknowledges support from the NSF Graduate Research Fellowship Program (DGE-1449440). Work performed at the University of Ottawa is graciously supported by the University of Ottawa, the Natural Sciences and Engineering Research Council of Canada, and the Canadian Foundation for Innovation. E.S. and M.K.W. thank the University of Bath for HPC facilities for computational time and for a Ph.D. studentship (W.J.M.B.), respectively. Publisher Copyright: {\textcopyright} 2022 American Chemical Society.",

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AU - Greer, Samuel M.

AU - Folli, Andrea

AU - Hill, Stephen

AU - Krewald, Vera

AU - Mahon, Mary F.

AU - Murphy, Damien M.

AU - Murugesu, Muralee

AU - Richards, Emma

AU - Suturina, Elizaveta

AU - Whittlesey, Michael K.

N1 - Funding Information: Work performed at the National High Magnetic Field Laboratory is supported by the National Science Foundation (NSF, DMR-1644779) and the State of Florida. Additional support from the NSF (DMR-2004732 to S.H.) is also gratefully acknowledged. S.M.G. acknowledges support from the NSF Graduate Research Fellowship Program (DGE-1449440). Work performed at the University of Ottawa is graciously supported by the University of Ottawa, the Natural Sciences and Engineering Research Council of Canada, and the Canadian Foundation for Innovation. E.S. and M.K.W. thank the University of Bath for HPC facilities for computational time and for a Ph.D. studentship (W.J.M.B.), respectively. Publisher Copyright: © 2022 American Chemical Society.

PY - 2022/1/24

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N2 - 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.

AB - 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.

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JF - Inorganic Chemistry

IS - 3

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

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