A Porous Metal–Organic Framework Assembled by [Cu(30)] Nanocages: Serving as Recyclable Catalysts for CO(2) Fixation with Aziridines

Based on a novel ligand 5‐(2,6‐bis(4‐carboxyphenyl)pyridin‐4‐yl)isophthalic acid (H(4)BCP) with large skeletons, a unique porous framework {[Cu(2)(BCP)(H(2)O)(2)]·3DMF}(n) (1) assembled by nano‐sized and censer‐like [Cu(30)] cages is successfully obtained and structurally characterized. In 1, the large 1D channel in frameworks and window size in the nanocages can enrich methylene blue and capture CO(2), exhibiting the promising applications in environmental protection. More importantly, the explorations on the cycloaddition reaction of CO(2) and aziridines with various substituents suggest that 1 can serve as an efficient heterogeneous catalyst for CO(2) conversion with aziridines in a solvent‐free system, which can be reused at least ten times without any obvious loss in catalytic activity. This is the first example of metal–organic framework (MOF)‐based catalysts in converting CO(2) into high‐value oxazolidinones through activating aziridines and CO(2), further extending the applications of MOFs materials in catalysis.