Porous molecular crystals sustained by hydrogen bonds and/or weaker connections are an intriguing type of adsorbents, but they rarely demonstrate efficient adsorptive separation because of poor structural robustness and tailorability. Herein, we report a porous molecular crystal based on hydrogen-bonded cyclic dinuclear AgI complex, which exhibits exceptional hydrophobicity with a water contact angle of 134°, and high chemical stability in water at pH 2-13. The seemingly rigid adsorbent shows a pore-opening or nonporous-to-porous type butane adsorption isotherm and complete exclusion of isobutane, indicating potential molecular sieving. Quantitative column breakthrough experiments show slight co-adsorption of isobutane with an experimental butane/isobutane selectivity of 23, and isobutane can be purified more efficiently than for butane. In situ powder/single-crystal X-ray diffraction and computational simulations reveal that a trivial guest-induced structural transformation plays a critical role.
Keywords: adsorptive separation; hydrogen-bonded organic frameworks (HOFs); hydrophobicity; molecular sieve; single-crystal-to-single-crystal.
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