Antimony-ligated dysprosium single-molecule magnets as catalysts for stibine dehydrocoupling† †Electronic supplementary information (ESI) available: Synthetic details, spectroscopic characterization for all compounds, X-ray crystallography details and crystallographic information files, computational details. CCDC 1484570–1484573 and 1485316. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc04465d Click here for additional data file. Click here for additional data file.

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. [(h-Cp02Dy){m-Sb(H) Mes}]3 (1-Dy) and [(h -Cp02Dy)3{m-(SbMes)3Sb}] (2-Dy), which contain the stibinide ligand [Mes(H)Sb] and the unusual Zintl-like ligand [Sb4Mes3] 3 , respectively (Cp0 1⁄4 methylcyclopentadienyl; Mes 1⁄4 mesityl). The zero-field anisotropy barriers in 1-Dy and 2-Dy are Ueff 1⁄4 345 cm 1 and 270 cm , 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.