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Issue 22, 2020
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Fulvalene as a platform for the synthesis of a dimetallic dysprosocenium single-molecule magnet

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Abstract

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)(η55-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.

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

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Supplementary files

Article information


Submitted
09 Apr 2020
Accepted
15 May 2020
First published
18 May 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020,11, 5745-5752
Article type
Edge Article

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

M. He, F. Guo, J. Tang, A. Mansikkamäki and R. A. Layfield, Chem. Sci., 2020, 11, 5745 DOI: 10.1039/D0SC02033H

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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