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Design and construction of stable adsorbents for efficient separation and purification of natural gas and C2H2 is fundamentally important in the chemical industry, and hierarchical cage-based MOFs are attractive in this regard due to their intrinsic structural advantages. In this work, a cage-based MOF (termed ZJNU-15) assembled from a tetranuclear Cu4O-based SBU and an amine-functionalized N,O-mixed donor ligand was solvothermally constructed. Single-crystal X-ray diffraction studies showed that the resulting MOF incorporates two differ