Metallization‐Prompted Robust Porphyrin‐Based Hydrogen‐Bonded Organic Frameworks for Photocatalytic CO2 Reduction

Under topological guidance, the self‐assembly process based on a tetratopic porphyrin synthon results in a hydrogen‐bonded organic framework (HOF) with the predicted square layers topology (sql) but unsatisfied stability. Strikingly, simply introducing a transition metal in the porphyrin center does not change the network topology but drastically causes noticeable change on noncovalent interaction, orbital overlap, and molecular geometry, therefore ultimately giving rise to a series of metalloporphyrinic HOFs with high surface area, and excellent stability (intact after being soaked in boiling water, concentrated HCl, and heated to 270 °C). On integrating both photosensitizers and catalytic sites into robust backbones, this series of HOFs can effectively catalyze the photoreduction of CO2 to CO, and their catalytic performances greatly depend on the chelated metal species in the porphyrin centers. This work enriches the library of stable functional HOFs and expands their applications in photocatalytic CO2 reduction. Crystallographic and computational studies on a series of porphyrinic hydrogen‐bonded organic frameworks (HOFs) reveal that metallization of porphyrin centers greatly alters the orbital overlap of the adjacent porphyrin, the geometry of the molecule/layer, and the strength of noncovalent interactions. Therefore, metalloporphyrin HOFs exhibit much higher stability, surface area, and catalytic activity than metal‐free porphyrinic HOFs.