Precisely Embedding Active Sites into a Mesoporous Zr-Framework through Linker Installation for High-Efficiency Photocatalysis.

The pore engineering of microporous metal-organic frameworks (MOFs) has been extensively investigated in the past two decades, and an expansive library of functional groups has been introduced into various frameworks. However, the reliable procurement of MOFs possessing both a targeted pore size and preferred functionality together is less common. This is especially important since the applicability of many elaborately designed materials is often restricted by the small pore sizes of microporous frameworks. Herein, we designed and synthesized a mesoporous MOF based on Zr6 clusters and tetratopic carboxylate ligands, termed PCN-808. The accessible coordinatively unsaturated metal sites as well as the intrinsic flexibility of the framework make PCN-808 a prime scaffold for postsynthetic modification via linker installation. A linear ruthenium-based metalloligand was successfully and precisely installed into the walls of open channels in PCN-808 while maintaining the mesoporosity of the framework. The photocatalytic activity of the obtained material, PCN-808-BDBR, was examined in the aza-Henry reaction and demonstrated high conversion yields after six catalytic cycles. Furthermore, thanks to the mesoporous nature of the framework, PCN-808-BDBR also exhibits exceptional yields for the photocatalytic oxidation of dihydroartemisinic acid to artemisinin.