ABSTRACT Hydrogen‐bonded organic frameworks (HOFs) have emerged as a distinctive class of porous crystalline materials assembled through directional yet reversible H‐bonds. Their mild synthesis, dynamic structural behavior, and recyclability distinguish them from metal‐ and covalent‐organic frameworks, while also presenting challenges in achieving targeted synthesis. The incorporation of reticular chemistry has gradually transformed HOFs from empirical assemblies into systems governed by design principles. This minireview discusses the evolution from molecular connectivity to topological design, emphasizing how directional H‐bond pairs and well‐defined tecton geometry enable the construction of predictable and stable frameworks. It further summarizes recent advances in reticular strategies for enhancing stability, tuning pore environment and functionality, and introducing framework flexibility through reticular design. Together, these developments illustrate how the rational control of weak interactions is guiding HOF chemistry toward programmable, multifunctional porous materials.
Wang et al. (Thu,) studied this question.