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From geometric to charge-distribution symmetry: deeper insights into lifting the performance of dysprosium single-ion magnets

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Abstract

Crystal-field symmetry of lanthanide ions plays a critical role in suppressing quantum tunneling of magnetization (QTM) in single-molecule magnets (SMMs), but high-performance SMM design and modulation remain challenging only in view of the geometric symmetry of the first coordination sphere. Herein, two bis(semicarbazone)/bis(thiosemicarbazone)dysprosium single-ion magnets with pentagonal bipyramid geometry were reported, and bis(thiosemicarbazone)lanthanide complexes have never been reported to the best of our knowledge. They served as good archetypes to study the magneto-structural relationships based on the charge distribution The complex with more ideal geometric symmetry displays fast zero-field QTM with negligible “effective barrier”, owing to the defective charge distribution. By modulating the transverse crystal field via the replacement of the O sites with the less charged and larger radius S atoms, it results in lower geometric but higher charge-distribution symmetry, giving rise to the significant suppression of QTM and the enhancement of reversal barrier up to ca. 1,000 K. These results demonstrate that the charge-distribution symmetry can be chemically tailored by modification of the crystal field, which is essential for designing high-performance SMMs.

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Acknowledgements

This work was supported by the National Key Research and Development Program of China (2018YFA0306001), the National Natural Science Foundation of China (22073115, 22105230, 22131011, 21821003), and the Pearl River Talent Plan of Guangdong (2017BT01C161).

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Authors and Affiliations

  1. Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, School of Chemistry, Sun Yat-Sen University, Guangzhou, 510006, China

    Wei Deng, Ying-Qian Zhou, Shan-Nan Du, Ze-Yu Ruan, Si-Guo Wu, Jun-Liang Liu & Ming-Liang Tong

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  1. Wei Deng
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  2. Ying-Qian Zhou
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Correspondence to Jun-Liang Liu.

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The supporting information is available online at https://chem.scichina.com and https://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.

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Deng, W., Zhou, YQ., Du, SN. et al. From geometric to charge-distribution symmetry: deeper insights into lifting the performance of dysprosium single-ion magnets. Sci. China Chem. 66, 1989–1996 (2023). https://doi.org/10.1007/s11426-023-1563-5

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  • DOI: https://doi.org/10.1007/s11426-023-1563-5

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