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A Dysprosium Metallocene Single‐Molecule Magnet Functioning at the Axial Limit
Author(s) -
Guo FuSheng,
Day Benjamin M.,
Chen YanCong,
Tong MingLiang,
Mansikkamäki Akseli,
Layfield Richard A.
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201705426
Subject(s) - dysprosium , lanthanide , chemistry , coercivity , metallocene , crystallography , magnetic anisotropy , magnet , hysteresis , ion , magnetization , inorganic chemistry , condensed matter physics , magnetic field , polymerization , physics , organic chemistry , quantum mechanics , polymer
Abstraction of a chloride ligand from the dysprosium metallocene [(Cp ttt ) 2 DyCl] ( 1 Dy Cp ttt =1,2,4‐tri( tert ‐butyl)cyclopentadienide) by the triethylsilylium cation produces the first base‐free rare‐earth metallocenium cation [(Cp ttt ) 2 Dy] + ( 2 Dy ) as a salt of the non‐coordinating [B(C 6 F 5 ) 4 ] − anion. Magnetic measurements reveal that [ 2 Dy ][B(C 6 F 5 ) 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 2 Dy 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 M J value, with no significant mixing even in the higher doublets.