Hydrogen-bonded organic frameworks (HOFs), self-assembled from strategically pre-designed molecular tectons with complementary hydrogen-bonding patterns, are rapidly evolving into a novel and important class of porous materials. In addition to their common features shared with other functionalized porous materials constructed from modular building blocks, the intrinsically flexible and reversible H-bonding connections endow HOFs with straightforward purification procedures, high crystallinity, solution processability, and recyclability. These unique advantages of HOFs have attracted considerable attention across a broad range of fields, including gas adsorption and separation, catalysis, chemical sensing, and electrical and optical materials. However, the relatively weak H-bonding interactions within HOFs can potentially limit their stability and potential use in further applications. To that end, this Perspective highlights recent advances in the development of chemically and thermally robust HOF materials and systematically discusses relevant design rules and synthesis strategies to access highly stable HOFs.

Three MOFs based on unsymmetrical diisophthalates exhibit selective C2H2/CH4 and CO2/CH4 adsorption and their adsorption selectivity can be improved by alkoxy group functionalization.

A ligand conformation preorganization strategy was employed to design a hexacarboxylate ligand, and its corresponding copper-based MOF was constructed, exhibiting a novel topological structure and the potential for the separation and purification of acetylene and natural gas.