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

DOI Web Site Web Site 被引用文献8件
  • Fu‐Sheng Guo
    School of Chemistry The University of Manchester Oxford Road Manchester M13 9PL UK
  • Benjamin M. Day
    School of Chemistry The University of Manchester Oxford Road Manchester M13 9PL UK
  • Yan‐Cong Chen
    Key Laboratory of Bioinorganic and Synthetic Chemistry of the Ministry of Education School of Chemistry Sun-Yat Sen University Guangzhou 510275 P.R. China
  • Ming‐Liang Tong
    Key Laboratory of Bioinorganic and Synthetic Chemistry of the Ministry of Education School of Chemistry Sun-Yat Sen University Guangzhou 510275 P.R. China
  • Akseli Mansikkamäki
    Department of Chemistry Nanoscience Center University of Jyväskylä P.O. Box 35 Jyväskylä 40014 Finland
  • Richard A. Layfield
    School of Chemistry The University of Manchester Oxford Road Manchester M13 9PL UK

説明

<jats:title>Abstract</jats:title><jats:p>Abstraction of a chloride ligand from the dysprosium metallocene [(Cp<jats:sup>ttt</jats:sup>)<jats:sub>2</jats:sub>DyCl] (<jats:bold>1<jats:sub>Dy</jats:sub></jats:bold> Cp<jats:sup>ttt</jats:sup>=1,2,4‐tri(<jats:italic>tert</jats:italic>‐butyl)cyclopentadienide) by the triethylsilylium cation produces the first base‐free rare‐earth metallocenium cation [(Cp<jats:sup>ttt</jats:sup>)<jats:sub>2</jats:sub>Dy]<jats:sup>+</jats:sup> (<jats:bold>2<jats:sub>Dy</jats:sub></jats:bold>) as a salt of the non‐coordinating [B(C<jats:sub>6</jats:sub>F<jats:sub>5</jats:sub>)<jats:sub>4</jats:sub>]<jats:sup>−</jats:sup> anion. Magnetic measurements reveal that [<jats:bold>2<jats:sub>Dy</jats:sub></jats:bold>][B(C<jats:sub>6</jats:sub>F<jats:sub>5</jats:sub>)<jats:sub>4</jats:sub>] is an SMM with a record anisotropy barrier up to 1277 cm<jats:sup>−1</jats:sup> (1837 K) in zero field and a record magnetic blocking temperature of 60 K, including hysteresis with coercivity. The exceptional magnetic axiality of <jats:bold>2<jats:sub>Dy</jats:sub></jats:bold> 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 <jats:italic>M<jats:sub>J</jats:sub></jats:italic> value, with no significant mixing even in the higher doublets.</jats:p>

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