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Playing with Magnetic Anisotropy in Hexacoordinated Mononuclear Ni(II) Complexes, An Interplay Between Symmetry and Geometry

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Abstract

The magnetic anisotropy parameters of a hexacoordinate trigonally elongated Ni(II) complex with symmetry close to D3d are measured using field-dependent magnetization and High-Field and High-Frequency EPR spectroscopy (D = + 2.95 cm−1, |E/D| = 0.08 from EPR). Wave function based theoretical calculations reproduce fairly well the EPR experimental data and allows analysing the origin of the magnetic anisotropy of the complex. Calculations on model complexes allows getting insight into the origin of the large increase in the axial magnetic anisotropy (D) when the complex is brought to a prismatic geometry with a symmetry close to D3h.

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Notes

  1. It is worth noting that the model complex with Φ = 60° obtained by turning the twist angle of 1 by 120° keeps the pseudo D3d symmetry as complex 1. We checked that the ZFS parameters of the as obtained model (Φ = 60°) are almost identical (D = 4.2 cm−1, E = 0.16 cm−1 and E/D = 0.037) to those of 1, suggesting that (i) loosing the inversion symmetry does not affect the ZFS parameters and (ii) the model complex with Φ = 60° is a reasonable model for 1. For (Φ = 0°), the model complex has a σh symmetry plane

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Acknowledgments

We thank the CNRS (Centre National de la Recherche Scientifique), the Université Paris-Saclay for financial support. We also thank H. Weihe for provision of the EPR simulation softwares.

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Authors and Affiliations

  1. Laboratoire de Chimie et Physique Quantiques, Université de Toulouse III, 118, route de Narbonne, 31062, Toulouse, France

    Nicolas Suaud, Mohammed-Amine Bouammali & Nathalie Guihéry

  2. IPCMS-GMI, UMR CNRS 7504, 23, rue du Loess, B.P. 43, 67034, Strasbourg Cedex 2, France

    Guillaume Rogez

  3. Institut de Chimie Moléculaire et des Matériaux d’Orsay, CNRS, Université Paris-Saclay, 91405, Orsay, France

    Jean-Noël Rebilly & Talal Mallah

  4. Laboratoire National des Champs Magnétiques Intenses, UPR CNRS 3228, Univ. Grenoble Alpes, 25, avenue des Martyrs, B.P. 166, 38042, Grenoble Cedex 9, France

    Anne-Laure Barra

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  1. Nicolas Suaud
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Correspondence to Nathalie Guihéry, Anne-Laure Barra or Talal Mallah.

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Suaud, N., Rogez, G., Rebilly, JN. et al. Playing with Magnetic Anisotropy in Hexacoordinated Mononuclear Ni(II) Complexes, An Interplay Between Symmetry and Geometry. Appl Magn Reson 51, 1215–1231 (2020). https://doi.org/10.1007/s00723-020-01228-8

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  • DOI: https://doi.org/10.1007/s00723-020-01228-8

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