Metallization‐Prompted Robust Porphyrin‐Based Hydrogen‐Bonded Organic Frameworks for Photocatalytic CO 2 Reduction

Under the topological guidance, the self-assembly process based on tetratopic porphyrin synthon results in a HOF with the predicted square layers topology (sql) but unsatisfied stability. Strikingly, simply introducing transition metal in 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 in 270 oC). With 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 porphyrin centers. This work enriches the library of stable functional HOFs and expands their applications in photocatalytic CO2 reduction.