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Investigation of the magnetic anisotropy in a series of trigonal bipyramidal Mn(II) complexes

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Abstract

Understanding how the magnetic anisotropy in simple coordination complexes can be manipulated is instrumental to the development of single-molecule magnets (SMMs). Clear strategies can then be designed to control both the axial and transverse contributions to the magnetic anisotropy in such compounds, and allow them to reach their full potential. Here we show a strategy for boosting the magnetic anisotropy in a series of trigonal bipyramidal Mn(II) complexes – [MnCl3(HDABCO)(DABCO)] (1), [MnCl3(MDABCO)2]·[ClO4] (2), and [MnCl3(H2O)(MDABCO)] (3). These have been successfully synthesised using the monodentate [DABCO] and [MDABCO]+ ligands. Through static (DC) magnetic measurements and detailed theoretical investigation using ab initio methods, the magnetic anisotropy of each system has been studied. The calculations reveal that the rhombic zero-field splitting (ZFS) term (E) can be tuned as the symmetry around the Mn(II) ion is changed. Furthermore, an in silico investigation reveals a strategy to increase the axial ZFS parameter (D) of trigonal bipyramidal Mn(II) by an order of magnitude.

Graphical abstract: Investigation of the magnetic anisotropy in a series of trigonal bipyramidal Mn(ii) complexes

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Publication details

The article was received on 23 May 2019, accepted on 27 Jun 2019 and first published on 28 Jun 2019


Article type: Paper
DOI: 10.1039/C9DT02187F
Dalton Trans., 2019, Advance Article
  • Open access: Creative Commons BY license
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    Investigation of the magnetic anisotropy in a series of trigonal bipyramidal Mn(II) complexes

    M. A. Hay, A. Sarkar, K. E. R. Marriott, C. Wilson, G. Rajaraman and M. Murrie, Dalton Trans., 2019, Advance Article , DOI: 10.1039/C9DT02187F

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