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

Abstract A novel 3D metal‐organic framework BSF‐1 based on the closo‐dodecaborate cluster [B 12 H 12 ] 2− was readily prepared at room temperature by supramolecular assembly of CuB 12 H 12 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 N 2 , C 2 H 2 , C 2 H 4 , CO 2 , C 3 H 8 , C 2 H 6 , and CH 4 indicated excellent separation selectivities for C 3 H 8 /CH 4 , C 2 H 6 /CH 4 , and C 2 H 2 /CH 4 as well as moderately high separation selectivities for C 2 H 2 /C 2 H 4 , C 2 H 2 /CO 2 , and CO 2 /CH 4 . Moreover, the practical separation performance of C 3 H 8 /CH 4 and C 2 H 6 /CH 4 was confirmed by dynamic breakthrough experiments. The good cyclability and high water/thermal stability render it suitable for real industrial applications.