Issue 40, 2021

Magnetic anisotropies of Ho(iii) and Dy(iii) single-molecule magnets experimentally determined via polarized neutron diffraction

Abstract

We present the magnetic anisotropy of two isostructural pentagonal-bipyramidal complexes, [Ln(H2O)5(HMPA)2]I3·2HMPA (HMPA = hexamethylphosphoramide, Ln = Dy, Ho). Using ac magnetic susceptibility measurements, we find magnetic relaxation barriers of 600 K and 270 K for the Dy- and Ho-compounds, respectively. This difference is supported by polarized neutron diffraction (PND) measured at 5 K and 1 T which provides the first experimental evidence that the transverse elements in the magnetic anisotropy of the Ho-analogue are significant, whereas the Dy-analogue has a near-axial magnetic anisotropy with vanishing transverse contributions. The coordination geometries of the two complexes are highly similar, and we attribute the loss of strong magnetic axiality as expressed in the atomic susceptibility tensors from PND, as well as the smaller relaxation barrier in the Ho-complex compared to the Dy-complex, to the less favorable interaction of the pentagonal bipyramidal crystal field with the characteristics of the Ho(III) 4f-charge distribution.

Graphical abstract: Magnetic anisotropies of Ho(iii) and Dy(iii) single-molecule magnets experimentally determined via polarized neutron diffraction

Supplementary files

Article information

Article type
Paper
Submitted
14 Jun 2021
Accepted
01 Sep 2021
First published
02 Sep 2021
This article is Open Access
Creative Commons BY license

Dalton Trans., 2021,50, 14207-14215

Magnetic anisotropies of Ho(III) and Dy(III) single-molecule magnets experimentally determined via polarized neutron diffraction

E. A. Klahn, A. M. Thiel, R. B. Degn, I. Kibalin, A. Gukassov, C. Wilson, A. B. Canaj, M. Murrie and J. Overgaard, Dalton Trans., 2021, 50, 14207 DOI: 10.1039/D1DT01959G

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