Abstract
Two structurally dissimilar 3d-4f cages having the formulae [(CoIII)3Gd4(μ3-OH)2(CO3) (O2CtBu)11(teaH)3]·5H2O (1) and [(CoIII)3Dy3(μ3-OH)4(O2CtBu)6(teaH)3]·(NO3)2·H2O (2) have been isolated under similar reaction conditions and stoichiometry of the reactants. The most important factor for structural diversity seems to be the incorporation of one μ3-carbonate anion in 1 and not in 2. Co atoms are in a +3 oxidation state in both complexes, as shown by the Bond Valence Sum (BVS) calculations and bond lengths, and as further supported by magnetic measurements. Co3Gd4 displays a significant magnetocaloric effect (−∆Sm = 25.67 J kg−1 K−1), and Co3Dy3 shows a single molecule magnet (SMM) behavior.
Highlights
In the field of magnetochemistry, molecular nanomagnets based on Gadolinium show magnetic refrigeration based on the magnetocaloric effect (MCE) [16,17,18,19]
Some of the molecular magnetic aggregates that are based on Dysprosium are useful as single-molecule magnets (SMMs) [20,21,22,23,24,25,26,27,28,29,30]
3d-Ln cages comprised of GdIII ions are suitable as magnetic refrigerants [11,12,13,14,15,46,47,48], and those with DyIII ions are ideal for SMM behaviour [31,32,33,34,35,36,37,38,39,40,41,42,43,44,45]
Summary
In the field of magnetochemistry, molecular nanomagnets based on Gadolinium show magnetic refrigeration based on the magnetocaloric effect (MCE) [16,17,18,19]. The inclusion of 4f ions (e.g., Dy3+ , Tb3+ , etc.) with 3d metals in nanosized systems (3d–4f approach) has been used to incorporate a large number of unpaired f electrons and high intrinsic magnetic anisotropy to obtain SMMs. SMMs based on DyIII exceed those of other LnIII -based SMMs, most likely due to their larger mJ state (mJ = ±15/2), which could lead to an appreciable magnetic moment. 3d-Ln cages comprised of GdIII ions are suitable as magnetic refrigerants [11,12,13,14,15,46,47,48], and those with DyIII ions (anisotropic) are ideal for SMM behaviour [31,32,33,34,35,36,37,38,39,40,41,42,43,44,45]
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