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

Abstract

AbstractThe 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.