Fluoride-Bridged {GdIII3MIII2} (M=Cr, Fe, Ga) Molecular Magnetic Refrigerants

Kasper Steen Pedersen, Giulia Lorusso, Juan José Morales, Thomas Weyhermüller, Stergios Piligkos, Saurabh Kumar Singh, Dennis Larsen, Magnus Schau-Magnussen, Gopalan Rajaraman, Marco Evangelisti, Jesper Bendix

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

The reaction of fac‐[MIIIF3(Me3tacn)]⋅x H2O with Gd(NO3)3⋅5H2O affords a series of fluoride‐bridged, trigonal bipyramidal {GdIII3MIII2} (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.
Original languageEnglish
JournalAngewandte Chemie
Volume126
Issue number9
Pages (from-to)2426-2429
ISSN0044-8249
DOIs
Publication statusPublished - 2014
Externally publishedYes

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