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Herein, the concept of topological supramolecular complexation is proposed for the feasible fabrication of hierarchical microporosity with broad tunability in amorphous form. The 2.5\u2005nm metal\u2010organic polyhedra (MOP) are complexed with quadridentate ligands through hydrogen and coordination bonding while the mismatch between the MOPs\u2019 cuboctahedron and ligands\u2019 tetrahedron topology leads to frustrated packing with extrinsic microporosity. Amorphous supramolecular frameworks can be obtained that integrate the intrinsic microporosity of the MOPs with the extrinsic porosity from the frustrated packing. The topologies, sizes and flexibility of ligands as well as ligand\/MOP ratios are systemically varied, and the pore size distribution can be precisely adjusted. The hierarchical structures ranging from molecular packing to the morphologies of meso\u2010scale assemblies are probed using ultra\u2010small, small\u2010 and wide\u2010angle X\u2010ray scattering, enabling the quantitative evaluation of the micropores interconnectivity for the understanding of gas permeation performance. Gas separation membranes with permselectivity surpassing the Robeson upper bound can be designed. The findings not only give insight into the microscopic mechanism of supramolecular frustrated packing from topological design, but also pave new avenues for the cost\u2010effective fabrications of microporous frameworks.<\/jats:p>","DOI":"10.1002\/anie.202424238","type":"journal-article","created":{"date-parts":[[2025,1,28]],"date-time":"2025-01-28T12:09:20Z","timestamp":1738066160000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Topological Supramolecular Complexation of Metal\u2010Organic Polyhedra for Tunable Interconnected Hierarchical Microporosity in Amorphous Form"],"prefix":"10.1002","volume":"64","author":[{"given":"Yuan","family":"Liu","sequence":"first","affiliation":[{"name":"State Key Laboratory of Luminescent Materials and Devices &amp; South China Advanced Institute for Soft Matter Science and Technology Guangdong Basic Research Center of Excellence for Energy and Information Polymer Materials South China University of Technology  Guangzhou 510641 P. 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