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The newly emerging porous crystalline materials, covalent organic framework (COF) and hydrogen-bonded organic framework (HOF), are characterized by their large surface area, considerable structural diversity, and functional tailorability. Combining these properties, they are considered to have the potential for photocatalysis. This review summarizes their advantages and compatibility, particularly focusing on design strategies to overcome the existing issues of poor charge conductivity and deficient active sites. With representative examples of solar-driven hydrogen (H2) evolution and carbon dioxide (CO2) reduction, the exploration and expectation of such functional porous materials are presented. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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 CO 2 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 CO 2 reduction., (© 2021 Wiley-VCH GmbH.)