TY - JOUR
T1 - Fluoride-bridged {GdIII3MIII2} (M=Cr, Fe, Ga) molecular magnetic refrigerants
AU - Pedersen, Kasper S.
AU - Lorusso, Giulia
AU - Morales, Juan José
AU - Weyhermüller, Thomas
AU - Piligkos, Stergios
AU - Singh, Saurabh Kumar
AU - Larsen, Dennis
AU - Schau-Magnussen, Magnus
AU - Rajaraman, Gopalan
AU - Evangelisti, Marco
AU - Bendix, Jesper
PY - 2014/2/24
Y1 - 2014/2/24
N2 - The reaction of fac-[MIIIF3(Me3tacn)] ×x H2O with Gd(NO3)3×5H 2O 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. Molecular coolers: Even labile fluoride complexes (see picture; Gd purple, Cr/Fe/Ga orange, F green, O red) are useful precursors for polynuclear, fluoride-bridged 3d-4f systems. Molecular geometry enforces weak exchange interactions, which is rationalized computationally. This, in conjunction with a lightweight auxiliary ligand sphere, gives rise to extremely large magnetic entropy changes.
AB - The reaction of fac-[MIIIF3(Me3tacn)] ×x H2O with Gd(NO3)3×5H 2O 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. Molecular coolers: Even labile fluoride complexes (see picture; Gd purple, Cr/Fe/Ga orange, F green, O red) are useful precursors for polynuclear, fluoride-bridged 3d-4f systems. Molecular geometry enforces weak exchange interactions, which is rationalized computationally. This, in conjunction with a lightweight auxiliary ligand sphere, gives rise to extremely large magnetic entropy changes.
KW - density functional calculations
KW - fluoride ligands
KW - lanthanides
KW - magnetic properties
KW - magnetic refrigeration
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U2 - 10.1002/anie.201308240
DO - 10.1002/anie.201308240
M3 - Article
AN - SCOPUS:84894435310
SN - 1433-7851
VL - 53
SP - 2394
EP - 2397
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 9
ER -