University of Oulu

He, M., Guo, F., Tang, J., Mansikkamäki, A., Layfield, R. (2020) Fulvalene as a platform for the synthesis of a dimetallic dysprosocenium single-molecule magnet. Chemical Science, 11 (22), 5745-5752.

Fulvalene as a platform for the synthesis of a dimetallic dysprosocenium single-molecule magnet

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Author: He, Mian1; Guo, Fu-Sheng1; Tang, Jinkui2;
Organizations: 1Department of Chemistry, School of Life Sciences, University of Sussex, Brighton, BN1 9QR, UK
2Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Renmin Street 5626, 130022 Changchun, China
3NMR Research Unit, University of Oulu, P.O. Box 8000, FI-90014, Finland
Format: article
Version: published version
Access: open
Online Access: PDF Full Text (PDF, 0.7 MB)
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Language: English
Published: Royal Society of Chemistry, 2020
Publish Date: 2020-06-16


The dinucleating fulvalenyl ligand [1,1′,3,3′-(C₅tBu₂H₂)₂]2− (Fvtttt) was used to synthesize the dimetallic dysprosocenium cation [{Dy(η⁵-Cp*)}₂(μ-BH₄)(η⁵:η⁵-Fvtttt)]⁺ (3) as the salt of [B(C₆F₅)₄]− (Cp* = C₅Me₅). Compound [3][B(C₆F₅)₄] was obtained using a method in which the double half-sandwich complex [{Dy(BH₄)₂(THF)}₂(Fvtttt)] (1) was reacted with KCp* to give the double metallocene [{Dy(Cp*)(μ-BH₄)}₂(Fvtttt)] (2), followed by removal of a bridging borohydride ligand upon addition of [(Et₃Si)₂(μ-H)][B(C₆F₅)₄]. The dimetallic fulvalenyl complexes 1–3 give rise to single-molecule magnet (SMM) behaviour in zero applied field, with the effective energy barriers of 154(15) cm−1, 252(4) cm−1 and 384(18) cm−1, respectively, revealing a significant improvement in performance across the series. The magnetic properties are interpreted with the aid of ab initio calculations, which show substantial increases in the axiality of the crystal field from 1 to 2 to 3 as a consequence of the increasingly dominant role of the Fvtttt and Cp* ligands, with the barrier height and hysteresis properties being attenuated by the equatorial borohydride ligands. The experimental and theoretical results described in this study furnish a blueprint for the design and synthesis of poly-cationic dysprosocenium SMMs with properties that may surpass those of benchmark systems.

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Series: Chemical science
ISSN: 2041-6520
ISSN-E: 2041-6539
ISSN-L: 2041-6520
Volume: 11
Pages: 5745 - 5752
DOI: 10.1039/D0SC02033H
Type of Publication: A1 Journal article – refereed
Field of Science: 114 Physical sciences
116 Chemical sciences
Funding: We thank the University of Sussex, the ERC (CoG 646740), the EPSRC (EP/M022064/1), the National Natural Science Foundation of China (Grants 21525103 and 21871247) and the University of Oulu (Kvantum Institute). Computational resources were provided by CSC-IT Center for Science in Finland and the Finnish Grid and Cloud Infrastructure (persistent identifier urn:nbn:fi:research-infras-2016072533). JT and RAL also thank the Royal Society for a Newton Advanced Fellowship (NA160075).
Copyright information: © The Authors. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.