University of Oulu

J. P. Durrant, B. M. Day, J. Tang, A. Mansikkamäki, R. A. Layfield, Angew. Chem. Int. Ed. 2022, 61, e202200525; Angew. Chem. 2022, 134, e202200525,

Dominance of cyclobutadienyl over cyclopentadienyl in the crystal field splitting in dysprosium single-molecule magnets

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Author: Durrant, James P.1; Day, Benjamin M.1; Tang, Jinkui2;
Organizations: 1Department of Chemistry, University of Sussex Falmer, Brighton, BN1 9QR UK
2State Key Laboratory of Rare Earth Resource Utilization, Changchun, Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022 P.R. China
3NMR Research Unit, University of Oulu, P. O. Box 8000, 90014 Oulu, Finland
Format: article
Version: published version
Access: open
Online Access: PDF Full Text (PDF, 1.2 MB)
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Language: English
Published: John Wiley & Sons, 2022
Publish Date: 2022-07-19


Replacing a monoanionic cyclopentadienyl (Cp) ligand in dysprosium single-molecule magnets (SMMs) with a dianionic cyclobutadienyl (Cb) ligand in the sandwich complexes [(η⁴-Cb′′′′)Dy(η⁵-C₅Me₄tBu)(BH₄)]⁻ (1), [(η⁴-Cb′′′′)Dy(η⁸-Pn)K(THF)] (2) and [(η⁴-Cb′′′′)Dy(η⁸-Pn)]⁻ (3) leads to larger energy barriers to magnetization reversal (Cb′′′′=C₄(SiMe₃)₄, Pn=1,4-di(tri-isopropylsilyl)pentalenyl). Short distances to the Cb′′′′ ligands and longer distances to the Cp ligands in 1–3 are consistent with the crystal field splitting being dominated by the former. Theoretical analysis shows that the magnetic axes in the ground Kramers doublets of 1–3 are oriented towards the Cb′′′′ ligands. The theoretical axiality parameter and the relative axiality parameter Z and Zrel are introduced to facilitate comparisons of the SMM performance of 1–3 with a benchmark SMM. Increases in Z and Zrel when Cb′′′ replaces Cp signposts a route to SMMs with properties that could surpass leading systems.

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Series: Angewandte Chemie. International edition in English
ISSN: 1433-7851
ISSN-E: 1521-3773
ISSN-L: 1433-7851
Volume: 61
Issue: 17
Article number: e202200525
DOI: 10.1002/anie.202200525
Type of Publication: A1 Journal article – refereed
Field of Science: 114 Physical sciences
116 Chemical sciences
Funding: R.A.L. thanks the European Research Council (CoG RadMag, grant 646740) and the EPSRC (EP/M022064/1), and J.T. thanks the National Natural Science Foundation of China (grants 21525103 and 21871247). J.T. and R.A.L. thank the Royal Society for a Newton Advanced Fellowship to JT (NA160075). A.M. acknowledges funding provided by the Academy of Finland (grant no. 332294) and the University of Oulu (Kvantum Institute).
Academy of Finland Grant Number: 332294
Detailed Information: 332294 (Academy of Finland Funding decision)
Copyright information: © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.