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Abstract Soft porous coordination polymers (PCPs) have the remarkable ability to recognize similar molecules as a result of their structural dynamics. However, their guest‐induced gate‐opening behaviors often lead to issues with selectivity and separation efficiency, as co‐adsorption is nearly unavoidable. Herein, we report a strategy of a confined‐rotational shutter, in which the rotation of pyridyl rings within the confined nanospace of a halogen‐bonded coordination framework ( NTU‐88 ) creates a maximum aperture of 4.4 Å, which is very close to the molecular size of propyne (C 3 H 4 : 4.4 Å), but smaller than that of propylene (C 3 H 6 : 5.4 Å). This has been evidenced by crystallographic analyses and modelling calculations. The NTU‐88o (open phase of activated NTU‐88 ) demonstrates dedicated C 3 H 4 adsorption, and thereby leads to a sieving separation of C 3 H 4 /C 3 H 6 under ambient conditions. The integrated nature of high uptake ratio, considerable capacity, scalable synthesis, and good stability make NTU‐88 a promising candidate for the feasible removal of C 3 H 4 from C 3 H 4 /C 3 H 6 mixtures. In principle, this strategy holds high potential for extension to soft families, making it a powerful tool for optimizing materials that can tackle challenging separations with no co‐adsorption, while retaining the crucial aspect of high capacity.
Wan et al. (Mon,) studied this question.