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Issue 31, 2018
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Slow magnetic relaxation in octahedral low-spin Ni(iii) complexes

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Abstract

Herein we report the first examples of single-molecule magnet (SMM) behaviour in S = 1/2 Ni(III) complexes. We find that low-spin 3d7trans-[NiIII(cyclam)(X)2]Y complexes (cyclam = 1,4,8,11-tetraazacyclotetradecane; X and Y are singly charged anions) exhibit field-induced slow relaxation of magnetization for O-donor axial ligands (nitrate) but not for N-donor variants (isothiocyanate). Experimental and electronic structure computational investigations indicate that intrinsic spin polarisation of low-spin Ni(III) is modulated significantly by local coordination geometry and supramolecular interactions. Solid state dilution of Ni(III) with diamagnetic Co(III) ions forms a related complex salt, [NixCo1−x(cyclam)(NO3)2](NO3)·2HNO3 (0.1 < x < 1), which preserves slow magnetic dynamics, thus supporting a molecular component to slow relaxation. An initial analysis of magnetic relaxation lifetime fits best to a combination of Raman and direct relaxation processes.

Graphical abstract: Slow magnetic relaxation in octahedral low-spin Ni(iii) complexes

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Publication details

The article was received on 16 Oct 2017, accepted on 28 Jun 2018 and first published on 12 Jul 2018


Article type: Edge Article
DOI: 10.1039/C7SC04482H
Chem. Sci., 2018,9, 6564-6571
  • Open access: Creative Commons BY-NC license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

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    Slow magnetic relaxation in octahedral low-spin Ni(III) complexes

    I. Bhowmick, A. J. Roehl, J. R. Neilson, A. K. Rappé and M. P. Shores, Chem. Sci., 2018, 9, 6564
    DOI: 10.1039/C7SC04482H

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