A Microporous Metal‐Organic Framework Supramolecularly Assembled from a CuII Dodecaborate Cluster Complex for Selective Gas Separation

A novel 3D metal-organic framework BSF-1 based on the closo-dodecaborate cluster B12 H12 2- was readily prepared at room temperature by supramolecular assembly of CuB12 H12 and 1,2-bis(4-pyridyl)acetylene. The permanent microporous structure was studied by X-ray crystallography, powder X-ray diffraction, IR spectroscopy, thermogravimetric analysis, and gas sorption. The experimental and theoretical study of the gas sorption behavior of BSF-1 for N2 , C2 H2 , C2 H4 , CO2 , C3 H8 , C2 H6 , and CH4 indicated excellent separation selectivities for C3 H8 /CH4 , C2 H6 /CH4 , and C2 H2 /CH4 as well as moderately high separation selectivities for C2 H2 /C2 H4 , C2 H2 /CO2 , and CO2 /CH4 . Moreover, the practical separation performance of C3 H8 /CH4 and C2 H6 /CH4 was confirmed by dynamic breakthrough experiments. The good cyclability and high water/thermal stability render it suitable for real industrial applications.