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

被引:167
作者
Guo, Fu-Sheng [1 ]
Chen, Yan-Cong [1 ]
Mao, Ling-Ling [1 ]
Lin, Wei-Quan [1 ]
Leng, Ji-Dong [1 ]
Tarasenko, Robert [2 ,3 ]
Orendac, Martin [2 ,3 ]
Prokleska, Jan [4 ]
Sechovsky, Vladimir [4 ]
Tong, Ming-Liang [1 ]
机构
[1] Sun Yat Sen Univ, Sch Chem & Chem Engn, State Key Lab Optoelect Mat & Technol, Key Lab Bioinorgan & Synthet Chem,Minist Educ, Guangzhou 510275, Guangdong, Peoples R China
[2] Safarik Univ, Fac Sci, Ctr Low Temp Phys, Kosice 04154, Slovakia
[3] Inst Expt Phys, Kosice 04154, Slovakia
[4] Charles Univ Prague, Dept Condensed Matter Phys, Fac Math & Phys, CZ-12116 Prague 2, Czech Republic
关键词
anion-templates; cluster compounds; lanthanides; magnetic properties; ENHANCED MAGNETIC COOLERS; CRYSTAL-STRUCTURES; MOLECULAR COOLERS; CLUSTERS; GD; POLYNUCLEAR; COMPLEXES; FRAMEWORK; LN; CHEMISTRY;
D O I
10.1002/chem.201302093
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
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, {Gd-38(ClO4)(6)} (1) and {Gd48Cl2(NO3)} (2), characterized by single-crystal X-ray crystallography, infrared spectroscopy, and magnetic measurements. {Gd-38(ClO4)(6)}, encapsulating six ClO4- ions, features a cage core composed of twelve vertex-sharing {Gd-4} tetrahedrons and one Gd center dot center dot center dot 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 {Gd-4} tetrahedrons and six {Gd-5} pyramids. What is more, the cage-like {Gd-38} can be dynamically converted into the barrel-shaped {Gd-48} upon Cl- and NO3- stimulus. To our knowledge, it is the first time that the linear M-O-M' fashion and the unique mu(8)-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 N-Gd/M-W ratio (magnetic density), and the relatively compact crystal lattice (mass density).
引用
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页码:14876 / 14885
页数:10
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