Two-Dimensional Networks of Lanthanide Cubane-Shaped Dumbbells

The syntheses, structures, and magnetic properties are reported for three new lanthanide complexes, [LnIII4(μ3−OH)2(μ3−O)2(cpt)6(MeOH)6(H2O)]2 (Ln = Dy (1·15MeOH), Ho (2·14MeOH), and Tb (3·18MeOH)), based on 4-(4-carboxyphenyl)-1,2,4-triazole ligand (Hcpt). The three complexes were confirmed to be isomorphous by infrared spectroscopy and single-crystal X-ray diffraction. The crystal structure of 1 reveals that the eight-coordinate metal centers are organized in two cubane-shaped moieties composed of four DyIII ions each. All metal centers in the cubane core are bridged by two μ3-oxide and two μ3-hydroxide asymmetrical units. Moreover, each cubane is linked to its neighbor by two externally coordinating ligands, forming the dumbbell {DyIII4}2 moiety. Electrostatic interactions between the ligands of the triazole-bridged dimers form an extended supramolecular two-dimensional arrangement analogous to a metal-organic framework with quadrilateral spaces occupied by ligands from axial sheets and by four solvent molecules. The magnetic properties of the three compounds have been investigated using dc and ac susceptibility measurements. For 1, the static and dynamic data corroborate the fact that the {DyIII4} cubane-shaped core exhibits slow relaxation of its magnetization below 5 K associated with a single-molecule magnet behavior.