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Synthesis, structures and magnetic properties of cyano- and amide-bridged FeIII-LnIII tetranuclear heterometallic clusters

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Three FeIII 2LnIII 2 tetranuclear heterometallic clusters, [H4LGd(H2O)Tp*Fe(CN)3]2·8H2O·2MeOH (1) and [H4LLn(MeOH)Tp*Fe(CN)3]2·6MeOH·2MeCN (Ln = Tb and Dy for 2 and 3, respectively, H6L = N,N′-(2,6-pyridine-dicarboxyl)-disalicylhydrazide, Tp* = hydridotris(3,5dimethylpyrazol-1-yl)-borate), were synthesized by use of the [(Tp*)Fe(CN)3] unit as a metalloligand toward LnCl3 and H6L species. Structural analyses reveal that FeIII and LnIII ions in all complexes are connected to each other by one cyanide to form a heterobinuclear unit of [Ln(H4L)][(Tp*)Fe(CN)3], which is dimerized through Ln–N–C = O–Ln interaction. Magnetic susceptibility measurements show weak antiferromagnetic interactions between cyano-bridged FeIII and GdIII ions and amide-bridged GdIII ions are operative. Complex 1 displays the magnetocaloric effect with −ΔS m max = 12.70 J·kg−1·K−1 at 4.0 K for ΔH = 7 T. No single-molecule magnetic properties are observed for 2 or 3 down to 1.8 K.
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Keywords: 3d–4f; Cyano- and amide-bridged; magnetic properties; magnetocaloric effect; tetranuclear

Document Type: Research Article

Affiliations: 1: School of Chemistry & Molecular Engineering, Nanjing Tech University, Nanjing, P. R. China; 2: School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng, P. R. China

Publication date: April 3, 2019

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