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Fine‐Tuning of Structural Distortion and Magnetic Anisotropy by Organosulfonates in Octahedral Cobalt(II) Complexes

Fine‐Tuning of Structural Distortion and Magnetic Anisotropy by Organosulfonates in Octahedral... Precise modulation of the magnetic anisotropy of metal ions remains highly important for the development of high–performance single‐molecule magnets (SMMs). We herein reported the synthetic, structural, spectral, magnetic, and computational studies on four mononuclear CoII complexes in a distorted octahedral environment. The change of the organosulfonate anions triggers significant modification of the distorted octahedral CoN6 coordination sphere, which enables us to tackle the influence of the structural distortion on the magnetic anisotropy in these complexes. Magnetic measurements revealed that the four complexes possess easy–plane magnetic anisotropy with large and positive zero‐field splitting parameters, which decrease with the increasing distortion of the pseudo–octahedral CoII coordination geometry. This correlation was further confirmed by high–frequency/–field EPR (HF–EPR) spectra and theoretical calculations. Dynamic magnetic susceptibility measurements indicate that these complexes both exhibit slow magnetic relaxation under an external dc field, indicating the field‐induced single‐ion magnets (SIMs) of the four complexes. These results indicate that structural distortion plays an important role in the magnetic anisotropy of CoII complexes and should be carefully considered in the design of molecular complexes with high magnetic anisotropy. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Chinese Journal of Chemistry Wiley

Fine‐Tuning of Structural Distortion and Magnetic Anisotropy by Organosulfonates in Octahedral Cobalt(II) Complexes

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References (24)

Publisher
Wiley
Copyright
© 2022 SIOC, CAS, Shanghai, & WILEY‐VCH GmbH
eISSN
1614-7065
DOI
10.1002/cjoc.202200284
Publisher site
See Article on Publisher Site

Abstract

Precise modulation of the magnetic anisotropy of metal ions remains highly important for the development of high–performance single‐molecule magnets (SMMs). We herein reported the synthetic, structural, spectral, magnetic, and computational studies on four mononuclear CoII complexes in a distorted octahedral environment. The change of the organosulfonate anions triggers significant modification of the distorted octahedral CoN6 coordination sphere, which enables us to tackle the influence of the structural distortion on the magnetic anisotropy in these complexes. Magnetic measurements revealed that the four complexes possess easy–plane magnetic anisotropy with large and positive zero‐field splitting parameters, which decrease with the increasing distortion of the pseudo–octahedral CoII coordination geometry. This correlation was further confirmed by high–frequency/–field EPR (HF–EPR) spectra and theoretical calculations. Dynamic magnetic susceptibility measurements indicate that these complexes both exhibit slow magnetic relaxation under an external dc field, indicating the field‐induced single‐ion magnets (SIMs) of the four complexes. These results indicate that structural distortion plays an important role in the magnetic anisotropy of CoII complexes and should be carefully considered in the design of molecular complexes with high magnetic anisotropy.

Journal

Chinese Journal of ChemistryWiley

Published: Sep 15, 2022

Keywords: Cobalt; Solid‐state structures; Magnetic properties; Single‐molecule magnets; Magnetic anisotropy

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