Abstract

Summary Creating crystalline porous materials with large pores is typically challenging due to undesired interpenetration, staggered stacking, or weakened framework stability. Here, we report a pore size expansion strategy by “shape-matching” intermolecular π-π stacking interactions in a series of two-dimensional (2D) hydrogen-bonded organic frameworks (HOFs), HOF-10x (x = 0,1,2), self-assembled from pyrene-based tectons with systematic elongation of π-conjugated molecular arms. This strategy successfully avoids interpenetration or staggered stacking and expands the pore size of HOF materials to access mesoporous HOF-102, which features a surface area of ∼2,500 m2/g and the largest pore volume (1.3 cm3/g) to date among all reported HOFs. More importantly, HOF-102 shows significantly enhanced thermal and chemical stability as evidenced by powder X-ray diffraction and N2 isotherms after treatments in challenging conditions. Such stability enables the easy fabrication of a HOF-102/fiber composite for the efficient photochemical detoxification of a mustard gas simulant.

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