A Dysprosium Metallocene Single-Molecule Magnet Functioning at the Axial Limit
Guo, F.-S., Day, B. M., Chen, Y.-C., Tong, M.-L., Mansikkamäki, A., & Layfield, R. A. (2017). A Dysprosium Metallocene Single-Molecule Magnet Functioning at the Axial Limit. Angewandte Chemie International Edition, 56(38), 11445-11449. https://doi.org/10.1002/anie.201705426
Published inAngewandte Chemie International Edition
DisciplineEpäorgaaninen ja analyyttinen kemiaNanoscience CenterInorganic and Analytical ChemistryNanoscience Center
© 2017 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim.
Abstraction of a chloride ligand from the dysprosium metallocene [(Cpttt)2DyCl] (1Dy Cpttt=1,2,4‐tri(tert‐butyl)cyclopentadienide) by the triethylsilylium cation produces the first base‐free rare‐earth metallocenium cation [(Cpttt)2Dy]+ (2Dy) as a salt of the non‐coordinating [B(C6F5)4]− anion. Magnetic measurements reveal that [2Dy][B(C6F5)4] is an SMM with a record anisotropy barrier up to 1277 cm−1 (1837 K) in zero field and a record magnetic blocking temperature of 60 K, including hysteresis with coercivity. The exceptional magnetic axiality of 2Dy is further highlighted by computational studies, which reveal this system to be the first lanthanide SMM in which all low‐lying Kramers doublets correspond to a well‐defined MJ value, with no significant mixing even in the higher doublets.
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Related funder(s)Academy of Finland
Funding program(s)Academy Project, AoF
Additional information about fundingWe thank: the UK EPSRC (Fellowship to RAL, postdoctoral funding to B.M.D.); the European Commission (MSCA Fellowship to F.S.G.); the NSFC (YCC and MLT, projects 21620102002, 91422302); the Academy of Finland (funding for A.M., project 282499); and Prof. H. M. Tuononen (University of Jyväskylä) for providing computational resources.
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