Issue 3, 2017

Antimony-ligated dysprosium single-molecule magnets as catalysts for stibine dehydrocoupling

Abstract

Single-molecule magnets (SMMs) are coordination compounds that exhibit magnetic bistability below a characteristic blocking temperature. Research in this field continues to evolve from its fundamental foundations towards applications of SMMs in information storage and spintronic devices. Synthetic chemistry plays a crucial role in targeting the properties that could ultimately produce SMMs with technological potential. The ligands in SMMs are invariably based on non-metals; we now report a series of dysprosium SMMs (in addition to their magnetically dilute analogues embedded in yttrium matrices) that contain ligands with the metalloid element antimony as the donor atom, i.e. [(η5-Cp′2Dy){μ-Sb(H)Mes}]3 (1-Dy) and [(η5-Cp′2Dy)3{μ-(SbMes)3Sb}] (2-Dy), which contain the stibinide ligand [Mes(H)Sb] and the unusual Zintl-like ligand [Sb4Mes3]3−, respectively (Cp′ = methylcyclopentadienyl; Mes = mesityl). The zero-field anisotropy barriers in 1-Dy and 2-Dy are Ueff = 345 cm−1 and 270 cm−1, respectively. Stabilization of the antimony-ligated SMMs is contingent upon careful control of reaction time and temperature. With longer reaction times and higher temperatures, the stibine pro-ligands are catalytically dehydrocoupled by the rare-earth precursor complexes. NMR spectroscopic studies of the yttrium-catalysed dehydrocoupling reactions reveal that 1-Y and 2-Y are formed during the catalytic cycle. By implication, 1-Dy and 2-Dy should also be catalytic intermediates, hence the nature of these complexes as SMMs in the solid-state and as catalysts in solution introduces a strategy whereby new molecular magnets can be identified by intercepting species formed during catalytic reactions.

Graphical abstract: Antimony-ligated dysprosium single-molecule magnets as catalysts for stibine dehydrocoupling

Supplementary files

Article information

Article type
Edge Article
Submitted
06 10 2016
Accepted
21 11 2016
First published
21 11 2016
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2017,8, 2073-2080

Antimony-ligated dysprosium single-molecule magnets as catalysts for stibine dehydrocoupling

T. Pugh, N. F. Chilton and R. A. Layfield, Chem. Sci., 2017, 8, 2073 DOI: 10.1039/C6SC04465D

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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