Rhombus-Shaped Tetranuclear [Ln4] Complexes [Ln = Dy(III) and Ho(III)]: Synthesis, Structure, and SMM Behavior

The reaction of a new hexadentate Schiff base hydrazide ligand (LH3) with rare earth­(III) chloride salts in the presence of triethylamine as the base afforded two planar tetranuclear neutral complexes: [{(LH)2Dy4}­(μ2-O)4]­(H2O)8·2CH3OH·8H2O (1) and [{(LH)2Ho4}­(μ2-O)4]­(H2O)8·6CH3OH·4H2O (2). These neutral complexes possess a structure in which all of the lanthanide ions and the donor atoms of the ligand remain in a perfect plane. Each doubly deprotonated ligand holds two Ln­(III) ions in its two distinct chelating coordination pockets to form [LH­(Ln)2]4+ units. Two such units are connected by four [μ2-O]2– ligands to form a planar tetranuclear assembly with an Ln­(III)4 core that possesses a rhombus-shaped structure. Detailed static and dynamic magnetic analysis of 1 and 2 revealed single-molecule magnet (SMM) behavior for complex 1. A peculiar feature of the χM″ versus temperature curve is that two peaks that are frequency-dependent are revealed, indicating the occurrence of two relaxation processes that lead to two energy barriers (16.8 and 54.2 K) and time constants (τ0 = 1.4 × 10–6 s, τ0 = 7.2 × 10–7 s). This was related to the presence of two distinct geometrical sites for Dy­(III) in complex 1.