Programmable Merged‐Net Porphyrinic Metal–Organic Frameworks for Water Sorption

Abstract Porous materials have attracted considerable interest as water sorbents due to their potential in a broad range of water sorption‐related applications. Metal–organic frameworks (MOFs) are particularly notable for their high porosity and tunability. However, their limited hydrolytic stability often results in pore collapse, which significantly hinders their water sorption performance. To address this issue, an innovative design strategy based on reticular chemistry is essential to enhance structural stability and ensure efficient water sorption. Herein, a novel synthetic approach for constructing a merged‐net MOF structure using metallolinkers is introduced. Specifically, a porphyrin linker is employed to successfully synthesize a porphyrin‐based merged‐net MOF, UPF‐5. This MOF demonstrates significantly enhanced hydrolytic stability and improved water sorption performance while maintaining high pore volume. Additionally, the structure of UPF‐5 allows for the modification of accessible Zr 6 nodes, enabling control over the pore environments and fine‐tuning the water sorption properties. This programmable synthetic strategy for porphyrin‐based merged‐net MOFs not only significantly enhances the structural stability for practical applications, including water sorption, but also advances reticular chemistry by discovering unprecedented topologies in MOF chemistry.