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. 2017 Sep 11;56(38):11445-11449.
doi: 10.1002/anie.201705426. Epub 2017 Jul 13.

A Dysprosium Metallocene Single-Molecule Magnet Functioning at the Axial Limit

Fu-Sheng Guo  1 , Benjamin M Day  1 , Yan-Cong Chen  2 , Ming-Liang Tong  2 , Akseli Mansikkamäki  3 , Richard A Layfield  1
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A Dysprosium Metallocene Single-Molecule Magnet Functioning at the Axial Limit

Fu-Sheng Guo et al. Angew Chem Int Ed Engl. .

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Abstract

Abstraction of a chloride ligand from the dysprosium metallocene [(Cpttt )2 DyCl] (1Dy Cpttt =1,2,4-tri(tert-butyl)cyclopentadienide) by the triethylsilylium cation produces the first base-free rare-earth metallocenium cation [(Cpttt )2 Dy]+ (2Dy ) as a salt of the non-coordinating [B(C6 F5 )4 ]- anion. Magnetic measurements reveal that [2Dy ][B(C6 F5 )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.

Keywords: anisotropy; cyclopentadienyl ligands; dysprosium; organometallic compounds; single-molecule magnets.

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