Dinuclear Tb and Dy complexes supported by hybrid Schiff-base/calixarene ligands: synthesis, structures and magnetic properties

The synthesis of the new lanthanide complexes [HNEt$_{3}$][Dy$_{2}$(HL$^{1}$)(L$^{1}$)] (5), and [Ln$_{2}$(L$_{2}$)$_{2}$] (Ln = Tb$^{III}$ (7), Dy$^{III}$ (8)) supported by the hybrid Schiff-base/calix[4]arene ligands H$_{4}$L$^{1}$ (25-[2-((2-methylphenol)imino)ethoxy]-26,27,28-trihydroxy-calix[4]arene) and H$_{3}$L$^{2}$ (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 NO$_{4}$Ln(μ-O)$_{2}$LnO$_{4}$N (5) or N$_{2}$O$_{3}$Ln(μ-O)$_{2}$LnO$_{3}$N$_{2}$ cores (7, 8) with seven-coordinated Ln$^{3+}$ 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.