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Fluoride-bridged {GdIII3MIII2} (M=Cr, Fe, Ga) molecular magnetic refrigerants

AuthorsLorusso, Giulia; Morales, Juan José; Evangelisti, Marco ; Bendix, Jesper
KeywordsMagnetische Kühlung
Magnetische Eigenschaften
Issue Date2014
CitationAngewandte Chemie - International Edition 52(40): 10458-10462 (2013)
AbstractThe reaction of fac-[MIIIF3(Me3tacn)] ×x H2O with Gd(NO3)3×5H 2O affords a series of fluoride-bridged, trigonal bipyramidal {GdIII 3MIII 2} (M=Cr (1), Fe (2), Ga (3)) complexes without signs of concomitant GdF3 formation, thereby demonstrating the applicability even of labile fluoride-complexes as precursors for 3d-4f systems. Molecular geometry enforces weak exchange interactions, which is rationalized computationally. This, in conjunction with a lightweight ligand sphere, gives rise to large magnetic entropy changes of 38.3 J kg-1 K-1 (1) and 33.1 J kg-1 K-1 (2) for the field change 7 T→0 T. Interestingly, the entropy change, and the magnetocaloric effect, are smaller in 2 than in 1 despite the larger spin ground state of the former secured by intramolecular Fe-Gd ferromagnetic interactions. This observation underlines the necessity of controlling not only the ground state but also close-lying excited states for successful design of molecular refrigerants.
Descriptionet al.
Publisher version (URL)http://dx.doi.org/10.1002/anie.201308240
Identifiersdoi: 10.1002/anie.201308240
issn: 1433-7851
e-issn: 1521-3773
Appears in Collections:(ICMA) Artículos
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