Endowing Porphyrinic Metal-Organic Frameworks with High Stability by a Linker Desymmetrization Strategy

The fabricating of metal-organic frameworks (MOFs) that integrate high stability and functionality remains a long-term pursuit yet a great challenge. Herein, we develop a linker desymmetrization strategy to construct highly stable porphyrinic MOFs, namely, USTC-9 (USTC represents the University of Science and Technology of China), presenting the same topological structure as the well-known PCN-600 that readily loses crystallinity in air or upon conventional activation. For USTC-9, the involved porphyrinic linker (TmCPP-M) with carboxylate groups located in the meta-position presents a chair-shaped conformation with lower C₂ symmetry than that (D₄) of the common porphyrinic carboxylate (TCPP) linker in PCN-600. As a result, the wrinkled and interlocked linker arrangements collectively contribute to the remarkable stability of USTC-9. Given the high stability and porosity as well as Lewis acidity, USTC-9(Fe) demonstrates its excellent performance toward catalytic CO₂ cycloaddition with diverse epoxides at moderate temperature and atmospheric pressure.