Record Complexity in the Polycatenation of Three Porous Hydrogen-Bonded Organic Frameworks with Stepwise Adsorption Behaviors.

Hydrogen-bonded organic frameworks (HOFs) show great potential in many applications, but few structure-property correlations have been explored in this field. In this work, we report that self-assembly of a rigid and planar ligand gives rise to flat hexagonal honeycomb motifs which are extended into undulated two-dimensional (2D) layers and finally generate three polycatenated HOFs with record complexity. This kind of undulation is absent in the 2D layers built from a very similar but nonplanar ligand, indicating that a slight torsion of ligand produces overwhelming structural change. This change delivers materials with unique stepwise adsorption behaviors under a certain pressure originating from the movement between mutually interwoven hexagonal networks. Meanwhile, high chemical stability, phase transformation, and preferential adsorption of aromatic compounds were observed in these HOFs. The results presented in this work would help us to understand the self-assembly behaviors of HOFs and shed light on the rational design of HOF materials for practical applications.