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Anion-templated assembly and magnetocaloric properties of a nanoscale {Gd38} cage versus a {Gd48} barrel.
- Source :
-
Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2013 Oct 25; Vol. 19 (44), pp. 14876-85. Date of Electronic Publication: 2013 Sep 17. - Publication Year :
- 2013
-
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 N(Gd)/M(W) ratio (magnetic density), and the relatively compact crystal lattice (mass density).<br /> (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Details
- Language :
- English
- ISSN :
- 1521-3765
- Volume :
- 19
- Issue :
- 44
- Database :
- MEDLINE
- Journal :
- Chemistry (Weinheim an der Bergstrasse, Germany)
- Publication Type :
- Academic Journal
- Accession number :
- 24105852
- Full Text :
- https://doi.org/10.1002/chem.201302093