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Anion-Templated Assembly and Magnetocaloric Properties of a Nanoscale {Gd38} Cage versus a {Gd48} Barrel.
- Source :
-
Chemistry - A European Journal . Oct2013, Vol. 19 Issue 44, p14876-14885. 10p. - Publication Year :
- 2013
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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). [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 09476539
- Volume :
- 19
- Issue :
- 44
- Database :
- Academic Search Index
- Journal :
- Chemistry - A European Journal
- Publication Type :
- Academic Journal
- Accession number :
- 91103274
- Full Text :
- https://doi.org/10.1002/chem.201302093