Dinuclear Tb and Dy Complexes Supported by Hybrid Schiff-base/calixarene Ligands: Synthesis, Structures and Magnetic Properties

The synthesis of the new lanthanide complexes [HNEt3][Dy2(HL1)(L1)] (5), and [Ln2(L2)2] (Ln = TbIII (7), DyIII (8)) supported by the hybrid Schiff-base/calix[4]arene ligands H4L1 (25-[2-((2-methylphenol)imino)ethoxy]-26,27,28-trihydroxy-calix[4]arene) and H3L2 (25-[2-((2-methylpyridine)imino)ethoxy]-26,27,28-trihydroxy-calix[4]arene) are reported. Spectroscopic data (for 5) and X-ray crystallographic analysis (for 7·4MeCN, 8·4MeCN) reveal the presence of dimeric structures, featuring doubly-bridged NO4Ln(μ-O)2LnO4N (5) or N2O3Ln(μ-O)2LnO3N2 cores (7, 8) with seven-coordinated Ln3+ ions. The magnetic properties of polycrystalline samples of 5, 7 and 8 were studied by variable temperature dc and ac magnetic susceptibility measurements. The χ''(T) vs. T plots show no maxima in zero field, but the maxima can be detected under a 3 kOe dc field. The relaxation times τ obey the Arrhenius law above 5 K. Anisotropy barriers of ∼18 cm-1 (26 K) for 5 and ∼23 cm-1 (33 K) for 8 were determined.