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

Content Provider	Royal Society of Chemistry (RSC)
Author	Chilton, Nicholas F. Pugh, Thomas Layfield, Richard A.
Copyright Year	2017
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.
Starting Page	2073
Ending Page	2080
Page Count	8
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	8
Issue Number	3
Journal	Chemical Science
DOI	10.1039/c6sc04465d
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Subscribed
Subject Keyword	Μ-opioid receptor Ligand Antimony Dysprosium Stibine Metalloid Bistability Anisotropy Mesitylene Nuclear magnetic resonance Chemical synthesis Yttrium Spintronics Catalytic cycle
Content Type	Text
Resource Type	Article
Subject	Chemistry

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