Pillared-layer cluster organic frameworks constructed from nanoscale Ln10 and Cu16 clusters.

Abstract

Two pillared-layer cluster organic frameworks, [Ln5(μ3-OH)4(μ-H2O)Cu8I8L11]·H2O (L = 4-pyridin-4-yl-benzoate; Ln = Dy(1), Eu(2)), have been made by employing lanthanide oxide and copper(I) halide as the source of lanthanide and transitional metal under hydrothermal condition. Compared to the pillared-layer frameworks constructed from heterometallic layers and organic pillars, these two compounds are derived from lanthanide cluster organic layers and copper(I) halide cluster motifs. Thus, there are two distinct types of inorganic metal connectors in the structure, one is hydroxo lanthanide [Ln10(μ3-OH)8](22+) (Ln10) cluster, and the other is copper(I) halide [Cu16I16] (Cu16) cluster. The rational assembly of these two inorganic connectors and organic linear linkers leads to the formation of the two complexes here. To the best of our knowledge, they appear to be the first 3D frameworks constructed from decanuclear hydroxo lanthanide clusters. From the topological point of view, these compounds represent an intriguing example of a binodal (8,14)-connected net considering the Ln10 and Cu16 connectors as the nodes, revealing that they are typical high dimensional frameworks with high connected net based on high nuclearity nodes. Furthermore, elemental analysis, IR, TGA, PXRD, and UV-vis properties are also studied.