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

被引：949

作者：

Guo, Fu-Sheng ^{[1
]}

Day, Benjamin M. ^{[1
]}

Chen, Yan-Cong ^{[2
]}

Tong, Ming-Liang ^{[2
]}

Mansikkamaki, Akseli ^{[3
]}

Layfield, Richard A. ^{[1
]}

机构：

[1] Univ Manchester, Sch Chem, Oxford Rd, Manchester M13 9PL, Lancs, England

[2] Sun Yat Sen Univ, Key Lab Bioinorgan & Synthet Chem, Minist Educ, Sch Chem, Guangzhou 510275, Guangdong, Peoples R China

[3] Univ Jyvaskyla, Dept Chem, Nanosci Ctr, POB 35, Jyvaskyla 40014, Finland

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2017年 / 56卷 / 38期

基金：

英国工程与自然科学研究理事会; 芬兰科学院;

关键词：

anisotropy; cyclopentadienyl ligands; dysprosium; organometallic compounds; single-molecule magnets; ION MAGNET; SYMMETRY; COMPLEXES; ANISOTROPY; BLOCKING; LIGANDS; RELAXATION; BARRIERS; BEHAVIOR; FIELD;

D O I：

10.1002/anie.201705426

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The 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-(C6F5)(4)](-) anion. Magnetic measurements reveal that [2(Dy)][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 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.

引用

页码：11445 / 11449

页数：5

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