Syntheses, Structures, and Properties of Novel Cagelike Complexes Based on Dodecanuclear Lanthanide with a Large Cavity

The syntheses, crystal structures, thermal gravimetric analyses (TGA), and magnetic properties of three novel hybrid
organic−inorganic dodecanuclear lanthanide-based complexes, [Ln12Na(L)5 (HL) (μ4-NO3)6(μ3-OH)2(μ2-H2O)6(H2O)12]·(H2O)n (Ln
= La (1), n = 23.5; Pr (2) and Nd (3), n = 39; L = 2-hydroxy-5-methyl-m-phenylenedimethylenedinitrilotetraacetate anion), are
reported. X-ray diffraction analyses revealed that three complexes were isostructural, exhibited C3 symmetry, and crystallized in the
rhombohedral crystal system, space group R3̄. In 1−3, 12 lanthanide atoms regularly arrayed and aggregated into a closed capsule-like cage by anion-bridged ligands containing polycarboxylate, phenolate, nitrate, and hydroxyl groups. Remarkably, these nanosized
discrete molecular cages afford large three-compartment cavities with [Na(H2O)6]+ ions encapsulated in the center site.