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Anion-Templated Assembly and Magnetocaloric Properties of a Nanoscale {Gd38} Cage versus a {Gd48} Barrel

Authors

  • Fu-Sheng Guo,

    1. Key Laboratory of Bioinorganic and Synthetic Chemistry of the Ministry of Education, State Key Laboratory of Optoelectronic Materials and Technologies, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275 (P.R. China)
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  • Yan-Cong Chen,

    1. Key Laboratory of Bioinorganic and Synthetic Chemistry of the Ministry of Education, State Key Laboratory of Optoelectronic Materials and Technologies, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275 (P.R. China)
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  • Ling-Ling Mao,

    1. Key Laboratory of Bioinorganic and Synthetic Chemistry of the Ministry of Education, State Key Laboratory of Optoelectronic Materials and Technologies, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275 (P.R. China)
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  • Wei-Quan Lin,

    1. Key Laboratory of Bioinorganic and Synthetic Chemistry of the Ministry of Education, State Key Laboratory of Optoelectronic Materials and Technologies, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275 (P.R. China)
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  • Ji-Dong Leng,

    1. Key Laboratory of Bioinorganic and Synthetic Chemistry of the Ministry of Education, State Key Laboratory of Optoelectronic Materials and Technologies, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275 (P.R. China)
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  • Róbert Tarasenko,

    1. Centre of Low Temperature Physics Faculty of Science, P.J. Šafárik University and Institute of Experimental Physics, SAS Park Angelinum 9, 041 54 Košice (Slovakia)
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  • Prof. Dr. Martin Orendáč,

    1. Centre of Low Temperature Physics Faculty of Science, P.J. Šafárik University and Institute of Experimental Physics, SAS Park Angelinum 9, 041 54 Košice (Slovakia)
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  • Dr. Jan Prokleška,

    1. Faculty of Mathematics and Physics, Department of Condensed Matter Physics, Charles University, Ke Karlovu 5, CZ-12116 Prague 2 (Czech Republic)
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  • Prof. Dr. Vladimír Sechovský,

    1. Faculty of Mathematics and Physics, Department of Condensed Matter Physics, Charles University, Ke Karlovu 5, CZ-12116 Prague 2 (Czech Republic)
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  • Prof. Dr. Ming-Liang Tong

    Corresponding author
    1. Key Laboratory of Bioinorganic and Synthetic Chemistry of the Ministry of Education, State Key Laboratory of Optoelectronic Materials and Technologies, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275 (P.R. China)
    • Key Laboratory of Bioinorganic and Synthetic Chemistry of the Ministry of Education, State Key Laboratory of Optoelectronic Materials and Technologies, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275 (P.R. China)

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Abstract

The comprehensive study reported herein provides compelling evidence that anion templates are the main driving force in the formation of two novel nanoscale lanthanide hydroxide clusters, {Gd38(ClO4)6} (1) and {Gd48Cl2(NO3)} (2), characterized by single-crystal X-ray crystallography, infrared spectroscopy, and magnetic measurements. {Gd38(ClO4)6}, encapsulating six ClO4 ions, features a cage core composed of twelve vertex-sharing {Gd4} tetrahedrons and one Gd⋅⋅⋅Gd pillar. When Cl and NO3 were incorporated in the reaction instead of ClO4, {Gd48Cl2(NO3)} is obtained with a barrel shape constituted by twelve vertex-sharing {Gd4} tetrahedrons and six {Gd5} pyramids. What is more, the cage-like {Gd38} can be dynamically converted into the barrel-shaped {Gd48} upon Cl and NO3 stimulus. To our knowledge, it is the first time that the linear M-O-M′ fashion and the unique μ8-ClO4 mode have been crystallized in pure lanthanide complex, and complex 2 represents the largest gadolinium cluster. Both of the complexes display large magnetocaloric effect in units of J kg−1 K−1 and mJ cm−3 K−1 on account of the weak antiferromagnetic exchange, the high NGd/MW ratio (magnetic density), and the relatively compact crystal lattice (mass density).

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