Sorting of C 4 Olefins with Interpenetrated Hybrid Ultramicroporous Materials by Combining Molecular Recognition and Size-Sieving

C olefin separations present one of the great challenges in hydrocarbon purifications owing to their similar structures, thus a single separation mechanism often met with limited success. Herein we report a series of anion-pillared interpenetrated copper coordination for which the cavity and functional site disposition can be varied in 0.2 Å scale increments by altering the anion pillars and organic linkers (GeFSIX-2-Cu-i (ZU-32), NbFSIX-2-Cu-i (ZU-52), GeFSIX-14-Cu-i (ZU-33)), which enable selective recognition of different C olefins. In these materials the rotation of the organic linkers is controlled to create a contracted flexible pore window that enables the size-exclusion of specific C olefins, while still adsorbing significant amounts of 1,3-butadiene (C H ) or 1-butene (n-C H ). Combining the molecular recognition and size-sieving effect, these materials unexpectedly realized the sieving of C H /n-C H , C H /iso-C H , and n-C H /iso-C H with high capacity.