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Metal-organic frameworks (MOFs) with HKUST-like tbo structures have been paid specific attention for gas sorption and separation because of their specific pore features. According to the geometric similarity of spirobifluorene and [Cu2(O2CR)4] paddlewheel secondary building units (Cu2 SBUs) in HKUST-1, we attempted to rationally construct a HKUST-like MOF by a substitution strategy. Using a judiciously designed octatopic carboxylate ligand, a copper-organic framework, JUC-220, was synthesized. The crystals of JUC-220 exhibited characteristic features in cubic with disorder, possibly due to the disorder substitution and high symmetry of tbo topology. Two related HKUST-like structure models were considered. Thanks to the suitable pore size and specific pore shapes, the adsorption selectivities of JUC-220 for C3H8/CH4 (5/85) and C2H6/CH4 (10/85) gas mixtures were as high as 736 and 46 respectively at 298 K and 1 bar. Specially, JUC-220 exhibited excellent trace adsorption performance of C3H8 and C2H6 as well as reverse adsorption behavior of C2H6/C2H4. Thus, JUC-220 serves as an example of HKUST-like MOF with disorder for light hydrocarbons separation and the implementation of substitution which can be used to explore more porous MOFs.
This research work was supported by the National Natural Science Foundation of China (Nos. 21871105, 21975096, and 21501064). We thank the staff at BL17B1 beamline of the National Facility for Protein Science in Shanghai (NFPS), Shanghai Advanced Research Institute, Chinese Academy of Sciences (CAS), for providing technical support in X-ray diffraction data collection. We also thank Professor Rajamani Krishna from University of Amsterdam for the breakthrough calculations.