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.

Cationic azole-based metal-organic frameworks (MOFs) with remarkable stability and unique pore environment have aroused great research interests. Meanwhile, flexible MOFs which can undergo pore-structure changes upon exposure to external stimuli are ideal materials for gas separation. However, introducing flexibility into the framework of cationic azole-based MOFs is rarely reported. Herein, we synthesized two stable isomorphic cationic MOFs (M-btz-as, M = Co, Ni) based on a linear azole ligand. After activated at high temperature under vacuum, M-btz-ht (M = Co, Ni) were obtained and both MOFs exhibited flexible features in which Co-btz is more flexible than Ni-btz. Different solvent-mediated activation methods were employed to explore their effects on structural flexibility and produced MOFs with different phases. Continuous phase transformation of Co-btz-e was verified by powder X-ray diffraction. In addition, these MOF phases possessed different gas separation abilities affected by their flexible frameworks, and Co-btz-ht exhibited the highest CO₂/CH₄ separation ability.