Binuclear and polynuclear cymantrenecarboxylate complexes of heavy lanthanides

Abstract

New binuclear cymantrenecarboxylate complexes of rare-earth metals, [Ln2(μ-O,η2-O2CCym)2(μ2-O,O′-O2CCym)2(η2-O2CCym)2(DMSO)4] (Ln = Tb (I), Dy (II); Cym = (η5-C5H4)Mn(CO)3) and [Ln2(μ2-O,O′-O2CCym)4(η2-NO3)2(DMSO)4] (Ln = Tb (III), Dy (IV)), are synthesized and characterized by X-ray diffraction analysis. The carboxylate clusters containing the Mn2+ ion, which is formed due to the destruction of the cymantrenenecarboxylate anion, [Tb4(μ3-OH)4(μ2-O,O′-O2CCym)6(H2O)3(THF)4][MnCl4] · 4CH2Cl2 · 6THF (V) with the cubane-like structure, and [Er2Mn(μ2-O2CCym)6(η2-O2CCym)2((MeO)3PO)4] · 2MePh (VI) with linear structure, are also obtained. The magnetism of complexes I, II, V, and VI is studied in a direct magnetic field. The magnetic properties of complexes II and VI are studied in direct and alternating magnetic fields. Complex II exhibits the properties of a single-molecule magnet. The thermal decomposition of complexes I–IV is studied by differential scanning calorimetry and thermogravimetric analysis. According to the X-ray diffraction analysis data, the final thermolysis products of complexes III and IV in air are multiferroics LnMn2O5.