%0 Journal Article
%T Molecular Sieving of Propyne/Propylene by a Scalable Nanoporous Crystal with Confined Rotational Shutters.
%A Wan J
%A Zhou HL
%A Hyeon-Deuk K
%A Chang IY
%A Huang Y
%A Krishna R
%A Duan J
%J Angew Chem Int Ed Engl
%V 62
%N 52
%D 2023 Dec 21
%M 37955415
%F 16.823
%R 10.1002/anie.202316792
%X 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 (C3 H4 : 4.4 Å), but smaller than that of propylene (C3 H6 : 5.4 Å). This has been evidenced by crystallographic analyses and modelling calculations. The NTU-88o (open phase of activated NTU-88) demonstrates dedicated C3 H4 adsorption, and thereby leads to a sieving separation of C3 H4 /C3 H6 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 C3 H4 from C3 H4 /C3 H6 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.