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

Using ferrocenecarboxylic acid (FcCO 2 H) and triethanolamine (H 3 ea) as ligands, the isostructural heterotrimetallic complexes [LnIII2CrIII2(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 ea = 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 {LnIII2CrIII2} 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.