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Issue 20, 2015
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Large and negative magnetic anisotropy in pentacoordinate mononuclear Ni(II) Schiff base complexes

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Abstract

A series of pentacoordinate Ni(II) complexes of the general formula [Ni(L5)] (1–6) with various pentadentate Schiff base ligands H2L5 (originating in a condensation of aromatic ortho-hydroxy-aldehydes and aliphatic triamines) was synthesized and characterized by X-ray structure analysis and magnetometry. The alternations of substituents on the H2L parent ligand resulted in the complexes with the geometry varying between the square-pyramid and trigonal-bipyramid. In the compounds whose chromophore geometry is closer to a trigonal-bipyramid, a large and negative uniaxial anisotropy (D = −64 cm−1) was identified. Moreover, the simple linear expression for the axial zero-field splitting (ZFS) parameter, D/cm−1 = 32.7(4.8) − 151(10)τ, was proposed, where τ (in degrees) stands for the Addison parameter. The results of magnetic analysis were also supported by ab initio CASSCF/NEVPT2 calculations of the ZFS splitting parameters D and E, and g tensors. Despite large and negative D-values of the reported compounds, slow relaxation of magnetization was not observed either in zero or non-zero static magnetic field, thus no single-molecule magnetic behaviour was detected.

Graphical abstract: Large and negative magnetic anisotropy in pentacoordinate mononuclear Ni(ii) Schiff base complexes

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Publication details

The article was received on 10 Feb 2015, accepted on 09 Apr 2015 and first published on 16 Apr 2015


Article type: Paper
DOI: 10.1039/C5DT00600G
Citation: Dalton Trans., 2015,44, 9551-9560
  • Open access: Creative Commons BY-NC license
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    Large and negative magnetic anisotropy in pentacoordinate mononuclear Ni(II) Schiff base complexes

    I. Nemec, R. Herchel, I. Svoboda, R. Boča and Z. Trávníček, Dalton Trans., 2015, 44, 9551
    DOI: 10.1039/C5DT00600G

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