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Experimental Determination of Magnetic Anisotropy in Exchange‐Bias Dysprosium Metallocene Single‐Molecule Magnets
Author(s) -
Meng YinShan,
Xiong Jin,
Yang MuWen,
Qiao YuSen,
Zhong ZhiQiang,
Sun HaoLing,
Han JunBo,
Liu Tao,
Wang BingWu,
Gao Song
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202004537
Subject(s) - dysprosium , metallocene , crystallography , magnet , molecule , chemistry , ab initio , lanthanide , magnetic anisotropy , ab initio quantum chemistry methods , materials science , magnetic field , ion , magnetization , inorganic chemistry , polymerization , physics , polymer , organic chemistry , quantum mechanics
We investigate a family of dinuclear dysprosium metallocene single‐molecule magnets (SMMs) bridged by methyl and halogen groups [Cp′ 2 Dy( μ ‐X)] 2 (Cp′=cyclopentadienyltrimethylsilane anion; 1 : X=CH 3 − ; 2 : X=Cl − ; 3 : X=Br − ; 4 : X=I − ). For the first time, the magnetic easy axes of dysprosium metallocene SMMs are experimentally determined, confirming that the orientation of them are perpendicular to the equatorial plane which is made up of dysprosium and bridging atoms. The orientation of the magnetic easy axis for 1 deviates from the normal direction (by 10.3°) due to the stronger equatorial interactions between Dy III and methyl groups. Moreover, its magnetic axes show a temperature‐dependent shifting, which is caused by the competition between exchange interactions and Zeeman interactions. Studies of fluorescence and specific heat as well as ab initio calculations reveal the significant influences of the bridging ligands on their low‐lying exchange‐based energy levels and, consequently, low‐temperature magnetic properties.