Exploiting supramolecular secondary building units (SSBUs) for developing porous crystalline materials represents an exciting breakthrough that extends the boundaries of reticular chemistry. However, shaping polynuclear clusters sustained by non-covalent interactions for the assembly of hydrogen-bonded frameworks remains a critical challenge. This study presents a novel strategy to stabilize SSBUs by tuning the π-stacking geometry of conjugated building blocks, facilitating the creation of hydrogen-bonded frameworks with tailored architectures for demanding gas separation. Specifically, parallel-displaced π-π stackings of aromatic heterocycles bearing carboxyls promote the formation of SSBUs bridged by ammonium cations [NH4+]8[COO-]8 (SSBU-4), enabling the assembly of hydrogen-bonded frameworks with permanent porosity and structural diversity influenced by the solvent effect. Comparatively, the non-heterocyclic building units exhibit geometrically- or energetically-unfavorable π stackings, resulting in fragile frameworks that collapse after removing disordered guests. Significantly, the heterocycle conjugated frameworks contain abundant open Brønsted acid N-H sites within pore channels, demonstrating remarkable NH3 adsorption ability among diverse industrial gases with a high capacity (275.7 mL/g, at 273 K, 100 kPa) as compared to reported porous molecular crystals.

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http://dx.doi.org/10.1002/anie.202500268DOI Listing

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