A novel 3D metal‐organic framework BSF‐1 based on the closo‐dodecaborate cluster [B12H12]2− was readily prepared at room temperature by supramolecular assembly of CuB12H12 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, C2H2, C2H4, CO2, C3H8, C2H6, and CH4 indicated excellent separation selectivities for C3H8/CH4, C2H6/CH4, and C2H2/CH4 as well as moderately high separation selectivities for C2H2/C2H4, C2H2/CO2, and CO2/CH4. Moreover, the practical separation performance of C3H8/CH4 and C2H6/CH4 was confirmed by dynamic breakthrough experiments. The good cyclability and high water/thermal stability render it suitable for real industrial applications.

The separation of C 2 H 2 /CO 2 is an important process in industry but challenged by the trade-off of capacity and selectivity owning to their similar physical properties and identical kinetic molecular size. We report the first example of symmetrically interpenetrated dodecaborate pillared MOF, ZNU-1, for benchmark selective separation of C 2 H 2 from CO 2 with ahigh C 2 H 2 capacity of 76.3 cm 3 g À1 and recordC 2 H 2 /CO 2 selectivity of 56.6 (298 K, 1bar) among all the robust porous materials without open metal sites.S ingle crystal structure analysis and modeling indicated that the interpenetration shifting from asymmetric to symmetric mode provided optimal pore chemistry with ideal synergistic "2+ +2" dihydrogen bonding sites for tight C 2 H 2 trapping.The exceptional separation performance was further evidenced by simulated and experimental breakthroughs with excellent recyclability and high productivity (2.4 mol kg À1 )o f9 9.5 %p urity C 2 H 2 during stepped desorption process.

Separation of acetylene (C2H2) from carbon dioxide (CO2) or ethylene (C2H4) is important in industry but limited by the low capacity and selectivity owing to their similar molecular sizes and physical properties. Herein, we report two novel dodecaborate‐hybrid metal–organic frameworks, MB12H12(dpb)2 (termed as BSF‐3 and BSF‐3‐Co for M=Cu and Co), for highly selective capture of C2H2. The high C2H2 capacity and remarkable C2H2/CO2 selectivity resulted from the unique anionic boron cluster functionality as well as the suitable pore size with cooperative proton‐hydride dihydrogen bonding sites (B−Hδ−⋅⋅⋅Hδ+−C≡C−Hδ+⋅⋅⋅Hδ−−B). This new type of C2H2‐specific functional sites represents a fresh paradigm distinct from those in previous leading materials based on open metal sites, strong electrostatics, or hydrogen bonding.

Ethylene (C2H4) purification from multi-component mixtures by physical adsorption is a great challenge in the chemical industry. Herein, we report a GeF62- anion embedded MOF (ZNU-6) with customized pore structure and pore chemistry for benchmark one-step C2H4 recovery from C2H2 and CO2. ZNU-6 exhibits significantly high C2H2 (1.53 mmol/g) and CO2 (1.46 mmol/g) capacity at 0.01 bar. Record high C2H4 productivity is achieved from C2H2/CO2/C2H4 mixtures in a single adsorption process under various conditions. The separation performance is retained over multiple cycles and under humid conditions. The potential gas binding sites are investigated by density functional theory (DFT) calculations, which suggest that C2H2 and CO2 are preferably adsorbed in the interlaced narrow channel with high aff0inity. In-situ single crystal structures with the dose of C2H2, CO2 or C2H4 further reveal the realistic host-guest interactions. Notably, rare C2H2 clusters are formed in the narrow channel while two distinct CO2 adsorption locations are observed in the narrow channel and the large cavity with a ratio of 1:2, which accurately account for the distinct adsorption heat curves.

A novel ultramicroporous boron cage-hybrid supramolecular framework BSF-2 comprising cluster [B12H11I]2− pillars was designed for highly selective light hydrocarbon separation.