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.