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Controlling magnetic anisotropy in a zero-dimensional S = 1 magnet using isotropic cation substitution
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Manson, Jamie, Curley, Samuel P. M., Williams, Robert C., Walker, David, Goddard, Paul, Ozarowski, Andrew, Johnson, Roger D., Vibhakar, Anuradha, Villa, Danielle, Rhodehouse, Melissa, Birnbaum, Serena M. and Singleton, John (2021) Controlling magnetic anisotropy in a zero-dimensional S = 1 magnet using isotropic cation substitution. Journal of the American Chemical Society, 143 (12). pp. 4633-4638. doi:10.1021/jacs.0c12516 ISSN 0002-7863.
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Official URL: http://dx.doi.org/10.1021/jacs.0c12516
Abstract
The [Zn1–xNix(HF2)(pyz)2]SbF6 (x = 0.2; pyz = pyrazine) solid solution exhibits a zero-field splitting (D) that is 22% larger [D = 16.2(2) K (11.3(2) cm–1)] than that observed in the x = 1 material [D = 13.3(1) K (9.2(1) cm–1)]. The substantial change in D is accomplished by an anisotropic lattice expansion in the MN4 (M = Zn or Ni) plane, wherein the increased concentration of isotropic Zn(II) ions induces a nonlinear variation in M-F and M-N bond lengths. In this, we exploit the relative donor atom hardness, where M-F and M-N form strong ionic and weak coordinate covalent bonds, respectively, the latter being more sensitive to substitution of Ni by the slightly larger Zn(II) ion. In this way, we are able to tune the single-ion anisotropy of a magnetic lattice site by Zn-substitution on nearby sites. This effect has possible applications in the field of single-ion magnets and the design of other molecule-based magnetic systems.
Item Type: | Journal Article | |||||||||||||||
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Subjects: | Q Science > QD Chemistry | |||||||||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Physics | |||||||||||||||
Library of Congress Subject Headings (LCSH): | Anisotropy, Isotropy subgroups, Symmetry groups | |||||||||||||||
Journal or Publication Title: | Journal of the American Chemical Society | |||||||||||||||
Publisher: | American Chemical Society | |||||||||||||||
ISSN: | 0002-7863 | |||||||||||||||
Official Date: | 31 March 2021 | |||||||||||||||
Dates: |
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Volume: | 143 | |||||||||||||||
Number: | 12 | |||||||||||||||
Page Range: | pp. 4633-4638 | |||||||||||||||
DOI: | 10.1021/jacs.0c12516 | |||||||||||||||
Status: | Peer Reviewed | |||||||||||||||
Publication Status: | Published | |||||||||||||||
Access rights to Published version: | Open Access (Creative Commons) | |||||||||||||||
Date of first compliant deposit: | 25 February 2021 | |||||||||||||||
Date of first compliant Open Access: | 23 March 2021 | |||||||||||||||
RIOXX Funder/Project Grant: |
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