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Herein, a microporous polyimide with high intrinsic free volume [PI\u2010TB\u2010NDI, naphthalenediimide (NDI) and Tr\u00f6ger's base (TB)] is synthesized for organic solvent nanofiltration. The resulting polymer showed high free volume because of fused aromatic rings and a twisted structure. Aromatic rings enhanced solvent resistance due to strong molecular interaction, but increased detrimental local tight packing as well. To suppress local tight packing without compromising the molecular interactions vital for stability, an\n                    <jats:italic>ortho<\/jats:italic>\n                    \u2010methyl group is deliberately introduced onto the TB unit to increase both intra\u2010 and inter\u2010molecular steric hindrance, imparting an H\u2010shaped TB\u2010NDI\u2010TB molecular stent. On the introduction of\n                    <jats:italic>ortho<\/jats:italic>\n                    \u2010methyl groups, the sub\u20100.4 nm ultra\u2010micropores are enlarged to ultra\u2010micropores (0.6\u20130.7 nm) to give the membrane with rich solvent\u2010accessible sub\u2010nanochannels. This resulted in an unprecedented enhancement of solvent permeability, with ethanol permeability 2\u20108 times greater than that of state\u2010of\u2010the\u2010art polymer membranes with similar selectivity. These findings advance the design strategy of microporous membranes with well\u2010tailored free volume without post\u2010treatments, enabling upscaling and efficient separation of precious species in organic solvents.\n                  <\/jats:p>","DOI":"10.1002\/advs.202416748","type":"journal-article","created":{"date-parts":[[2025,5,29]],"date-time":"2025-05-29T10:11:13Z","timestamp":1748513473000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Microporous Polymer Membranes: Molecular Stents Enhanced Solvent\u2010Accessibility for Organic Solvent Transport"],"prefix":"10.1002","volume":"12","author":[{"given":"Shuang","family":"Guo","sequence":"first","affiliation":[{"name":"MOE Key Laboratory of Macromolecular Synthesis and Functionalization MOE Engineering Research Center of Membrane and Water Treatment Technology Department of Polymer Science and Engineering Zhejiang University  Hangzhou 310027 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Water Treatment Technology Department of Polymer Science and Engineering Zhejiang University  Hangzhou 310027 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Weilin","family":"Feng","sequence":"additional","affiliation":[{"name":"MOE Key Laboratory of Macromolecular Synthesis and Functionalization MOE Engineering Research Center of Membrane and Water Treatment Technology Department of Polymer Science and Engineering Zhejiang University  Hangzhou 310027 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hukang","family":"Guo","sequence":"additional","affiliation":[{"name":"MOE Key Laboratory of Macromolecular Synthesis and Functionalization MOE Engineering Research Center of Membrane and Water Treatment Technology Department of Polymer Science and Engineering Zhejiang University  Hangzhou 310027 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ming","family":"Xie","sequence":"additional","affiliation":[{"name":"Department of Polymer Science and Engineering Department of Chemical Engineering University of Bath  Bath BA2 7AY UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yongbing","family":"Zhuang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Biochemical Engineering Institute of Process Engineering University of Chinese Academy of Sciences Chinese Academy of Sciences  Beijing 100190 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Young Moo","family":"Lee","sequence":"additional","affiliation":[{"name":"Department of Energy Engineering College of Engineering Hanyang University  Seoul 04763 South Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1553-4190","authenticated-orcid":false,"given":"Liping","family":"Zhu","sequence":"additional","affiliation":[{"name":"MOE Key Laboratory of Macromolecular Synthesis and Functionalization MOE Engineering Research Center of Membrane and Water 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