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Ligand-Conformer-Induced Formation of  Zirconium-Organic Framework  for Methane Storage and MTO Product Separation.

In pursuit of novel adsorbents with efficient adsorptive gas storage and separation capabilities remains highly desired and challenging. Although the documented zirconium-tricarboxylate-based metal-organic frameworks (MOFs) have displayed a variety of topologies encompassing underlying and geometry mismatch ones, the employed organic linkers are exclusively rigid and poorly presenting one type of conformation in the resultant structures. Herein, a used and semirigid tricarboxylate ligand of H3TATAB was judiciously selected to isolate a zirconium-based spe-MOF after the preliminary discovery of srl-MOF. Single-crystal X-ray diffraction reveals that the fully deprotonated TATAB linker in spe-MOF exhibits two distinct conformers, concomitant with popular Oh and rare S6 symmetrical Zr6 molecular building blocks, generating an unprecedented (3,3,12,12)-c nondefault topology. Specifically, the spe-MOF exhibits structurally higher complexity, hierarchical micropores, open metal sites free and rich electronegative groups on the pore surfaces, leading to relatively high methane storage capacity without considering the missing-linker defects and efficient MTO product separation performance.