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In this work, a gas molecular sieving effect in the liquid phase at sub\u20105 \u00c5ngstrom scale is created via sophisticated porosity tuning in calixarene\u2010derived porous liquids (PLs). Type\u2005II PLs are constructed via supramolecular complexation between the sodium salts of calixarene derivatives and crown ether solvents. The chemical structure variation and assembly behavior of the porous host upon PL construction are monitored by spectroscopy\u2010, X\u2010ray\u2010, and neutron\u2010scattering techniques. The presence of permanent porosity in calixarene\u2010derived PLs is verified by pressure swing gas uptake, altered CO\n                    <jats:sub>2<\/jats:sub>\n                    physisorption behavior, and molecular simulations. Sub\u20105 \u00c5ngstrom porosity tuning within the PL phase is achieved by introducing bulky substituted groups on the benzene ring of the calixarene host, which then greatly affects the dynamic motion and transport behavior of CO\n                    <jats:sub>2<\/jats:sub>\n                    molecules and the Xe uptake performance. The approach being demonstrated in this work represents a promising pathway to tune and leverage the porosity effect for enhanced gas uptake capacity and selectivity in liquid sorbents.\n                  <\/jats:p>","DOI":"10.1002\/anie.202421615","type":"journal-article","created":{"date-parts":[[2025,1,6]],"date-time":"2025-01-06T10:43:53Z","timestamp":1736160233000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":19,"title":["Sub\u20105 \u00c5ngstrom Porosity Tuning in Calixarene\u2010Derived Porous Liquids via Supramolecular Complexation Construction"],"prefix":"10.1002","volume":"64","author":[{"given":"Errui","family":"Li","sequence":"first","affiliation":[{"name":"Department of Chemistry University of Tennessee Knoxville  Knoxville TN 37996 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Arvind","family":"Ganesan","sequence":"additional","affiliation":[{"name":"Chemical Sciences Division Oak Ridge National Laboratory  Oak Ridge TN 37831 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hongjun","family":"Liu","sequence":"additional","affiliation":[{"name":"Department of Chemical and Biomolecular Engineering Vanderbilt University  Nashville TN 37235 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Alexander S.","family":"Ivanov","sequence":"additional","affiliation":[{"name":"Chemical Sciences Division Oak Ridge National Laboratory  Oak Ridge TN 37831 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lilin","family":"He","sequence":"additional","affiliation":[{"name":"Neutron Scattering Division Oak Ridge National Laboratory  Oak Ridge TN 37831 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Phattananawee","family":"Nalaoh","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Tennessee Knoxville  Knoxville TN 37996 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