Tetranuclear Cr–Ln ferrocenecarboxylate complexes with a defect-dicubane structure: synthesis, magnetism, and thermolysis - Archive ouverte HAL Access content directly
Journal Articles Dalton Transactions Year : 2021

Tetranuclear Cr–Ln ferrocenecarboxylate complexes with a defect-dicubane structure: synthesis, magnetism, and thermolysis

Abstract

Using ferrocenecarboxylic acid (FcCO 2 H) and triethanolamine (H 3 tea) as ligands, the isostructural heterotrimetallic complexes [Ln III 2 Cr III 2 (OH) 2 (FcCO 2) 4 (NO 3) 2 (Htea) 2 ]•2MePh•2THF (Ln = Tb (1), Dy (2), Ho (3), Er (4), and Y (5); Fc = (η 5-C 5 H 4)(η 5-C 5 H 5)Fe; H 3 tea = N(CH 2 CH 2 OH) 3) were obtained. In all of the complexes which possess a defective dicubane structure, two doubly deprotonated triethanolamine ligands chelate the chromium ions. However, during the synthesis of 1, an isomeric complex 1a in which Tb 3+ is chelated by triethanolamine as a tetradentate ligand, was also isolated as a few single crystals. Magnetic susceptibility measurements revealed dominant antiferromagnetic interactions in the {Ln III 2 Cr III 2 } cores of 1-4 leading to the formation of complexes with an uncompensated magnetic moment, while weak Cr-Cr ferromagnetic interactions were detected in the Y analogue. Complexes 1, 2, and 3 exhibit single-molecule magnet properties dominated by an Orbach-type relaxation mechanism with magnetization reversal barriers (Δ/k B) estimated around 54, 75, and 47 K, respectively. The Dy complex exhibits a magnetization hysteresis in an applied magnetic field at temperatures below 4 K. Thermolysis of the complexes was studied by TGA and DSC techniques; the final products obtained under an air atmosphere contain mixed oxide Cr 0.75 Fe 1.25 O 3 and heterotrimetallic oxide LnCr 1−x Fe x O 3 (with x ≈ 0.75) phases.
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Dates and versions

hal-03460616 , version 1 (01-12-2021)

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Pavel S Koroteev, Zhanna V Dobrokhotova, Andrey B Ilyukhin, Ekaterina V Belova, Alexey D Yapryntsev, et al.. Tetranuclear Cr–Ln ferrocenecarboxylate complexes with a defect-dicubane structure: synthesis, magnetism, and thermolysis. Dalton Transactions, 2021, 50, pp.16990 - 16999. ⟨10.1039/d1dt02562g⟩. ⟨hal-03460616⟩

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