{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,12]],"date-time":"2026-08-12T15:14:01Z","timestamp":1786547641606,"version":"build-2736575974"},"reference-count":80,"publisher":"American Chemical Society (ACS)","issue":"31","license":[{"start":{"date-parts":[[2026,7,28]],"date-time":"2026-07-28T00:00:00Z","timestamp":1785196800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100000288","name":"Royal Society","doi-asserted-by":"publisher","award":["RGF\\EA\\180077"],"award-info":[{"award-number":["RGF\\EA\\180077"]}],"id":[{"id":"10.13039\/501100000288","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100000288","name":"Royal Society","doi-asserted-by":"publisher","award":["UF160394"],"award-info":[{"award-number":["UF160394"]}],"id":[{"id":"10.13039\/501100000288","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100000781","name":"European Research Council","doi-asserted-by":"publisher","award":["787073"],"award-info":[{"award-number":["787073"]}],"id":[{"id":"10.13039\/501100000781","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100000848","name":"University of Edinburgh","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100000848","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100018694","name":"HORIZON EUROPE Marie Sklodowska-Curie Actions","doi-asserted-by":"publisher","award":["101198684"],"award-info":[{"award-number":["101198684"]}],"id":[{"id":"10.13039\/100018694","id-type":"DOI","asserted-by":"publisher"}]},{"name":"UK Research and Innovation (UKRI)","award":["MR\/V026070\/1"],"award-info":[{"award-number":["MR\/V026070\/1"]}]},{"DOI":"10.13039\/501100000266","name":"Engineering and Physical Sciences Research Council (EPSRC)","doi-asserted-by":"crossref","award":["EP\/X035859\/1"],"award-info":[{"award-number":["EP\/X035859\/1"]}],"id":[{"id":"10.13039\/501100000266","id-type":"DOI","asserted-by":"crossref"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,8,12]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Metal\u2013organic frameworks (MOFs) of the type MIL-53(M)-fum, where M3+ cations are connected by fumarate (fum) linkers in the canonical MIL-53 topology, have been investigated as possible adsorbents due to their structural rigidity, high porosity, and biologically endogenous organic linker. Examples reported to date are limited to those comprised of p-block metal ions (e.g., Al3+, Ga3+, and In3+); d-block metal ions (e.g., Fe3+ and Sc3+) tend to form MIL-88A(M) materials with the fumarate linker. Herein, we describe the solvent-induced self-assembly of MIL-53(Sc)-fum, by immersing MIL-88A(Sc) in water or aqueous solutions of N,N-dimethylformamide (DMF). Single-crystal X-ray diffraction confirms the solvent-selective formation of two different conformational isomers of MIL-53(Sc)-fum in this unusual MOF-to-MOF synthesis, and both are found to exhibit structural breathing, in contrast to the predominantly rigid p-block metal homologues. Furthermore, we show that the extent of flexibility can be tuned by postsynthetic cluster anion substitution. Refluxing MIL-53(Sc)-fum samples in methanol results in 40\u201350% exchange of \u03bc2\u2013OH units for \u03bc2-OCH3 groups, where the steric bulk holds the MOFs in a slightly more open pore configuration, enabling significant N2 adsorption at low pressures in contrast to the fully closed, unfunctionalized precursors. This study provides significant insight into MOF-to-MOF self-assembly, conformational isomerism in MOFs, and the effect of both metal ion and cluster anion substitution on structural flexibility, enabling careful tuning of highly porous MOFs from simple components.<\/jats:p>","DOI":"10.1021\/jacs.6c06041","type":"journal-article","created":{"date-parts":[[2026,8,4]],"date-time":"2026-08-04T13:13:50Z","timestamp":1785849230000},"page":"33206-33216","source":"Crossref","is-referenced-by-count":0,"title":["Cluster Anion Substitution\nTunes Flexibility and Porosity\nof MIL-53(Sc)-fum Conformational Isomers Isolated by Solvent-Induced\nMOF-to-MOF Self-Assembly"],"prefix":"10.1021","volume":"148","author":[{"given":"Catherine A.","family":"Walshe","sequence":"first","affiliation":[{"name":"University of Glasgow , , Joseph Black Building, University Avenue , ,","place":["Glasgow, U.K., G12 8QQ"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2740-7137","authenticated-orcid":true,"given":"Zachary H.","family":"Davis","sequence":"additional","affiliation":[{"name":"University of St Andrews , , ,","place":["St Andrews, U.K., KY16 9ST"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2980-2678","authenticated-orcid":true,"given":"Chi C.","family":"Hong","sequence":"additional","affiliation":[{"name":"University of Edinburgh , , King\u2019s Buildings, David Brewster Road , ,","place":["Edinburgh, U.K., EH9 3FJ"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4240-0224","authenticated-orcid":true,"given":"Thach N.","family":"Tu","sequence":"additional","affiliation":[{"name":"University of Glasgow , , Joseph Black Building, University Avenue , ,","place":["Glasgow, U.K., G12 8QQ"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1574-7476","authenticated-orcid":true,"given":"Sanliang","family":"Ling","sequence":"additional","affiliation":[{"name":"University of Nottingham , , University Park , ,","place":["Nottingham, U.K., NG7 2RD"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0090-5374","authenticated-orcid":true,"given":"Claire","family":"Wilson","sequence":"additional","affiliation":[{"name":"University of Glasgow , , Joseph Black Building, University Avenue , ,","place":["Glasgow, U.K., G12 8QQ"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3247-1803","authenticated-orcid":true,"given":"Joshua J. B.","family":"Levinsky","sequence":"additional","affiliation":[{"name":"University of Edinburgh , , King\u2019s Buildings, David Brewster Road , ,","place":["Edinburgh, U.K., EH9 3FJ"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4925-4557","authenticated-orcid":true,"given":"Claire L.","family":"Hobday","sequence":"additional","affiliation":[{"name":"University of Edinburgh , , King\u2019s Buildings, David Brewster Road , ,","place":["Edinburgh, U.K., EH9 3FJ"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4538-6782","authenticated-orcid":true,"given":"Sharon E.","family":"Ashbrook","sequence":"additional","affiliation":[{"name":"University of St Andrews , , ,","place":["St Andrews, U.K., KY16 9ST"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4767-6852","authenticated-orcid":true,"given":"Ross S.","family":"Forgan","sequence":"additional","affiliation":[{"name":"University of Glasgow , , Joseph Black Building, University Avenue , ,","place":["Glasgow, U.K., G12 8QQ"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,7,28]]},"reference":[{"issue":"6149","key":"2026081210073843000_cit1","doi-asserted-by":"publisher","first-page":"1230444","DOI":"10.1126\/science.1230444","article-title":"The Chemistry and\nApplications of Metal-Organic Frameworks","volume":"341","author":"Furukawa","year":"2013","journal-title":"Science"},{"issue":"2","key":"2026081210073843000_cit2","doi-asserted-by":"publisher","first-page":"933","DOI":"10.1021\/cr200304e","article-title":"Synthesis of Metal-Organic\nFrameworks (MOFs): Routes\nto Various MOF Topologies, Morphologies, and Composites","volume":"112","author":"Stock","year":"2012","journal-title":"Chem. Rev."},{"issue":"2","key":"2026081210073843000_cit3a","doi-asserted-by":"publisher","first-page":"498","DOI":"10.1039\/C0CS00031K","article-title":"Postsynthetic modification of metal\u2013organic\nframeworks\u2500a progress report","volume":"40","author":"Tanabe","year":"2011","journal-title":"Chem. Soc.\nRev."},{"issue":"5","key":"2026081210073843000_cit3b","doi-asserted-by":"publisher","first-page":"1315","DOI":"10.1039\/b802258p","article-title":"Postsynthetic modification of metal\u2013organic\nframeworks","volume":"38","author":"Wang","year":"2009","journal-title":"Chem. Soc. Rev."},{"issue":"7","key":"2026081210073843000_cit3c","doi-asserted-by":"publisher","first-page":"1046","DOI":"10.1021\/acscentsci.0c00690","article-title":"Postsynthetic Modification: An Enabling Technology\nfor the Advancement of Metal\u2013Organic Frameworks","volume":"6","author":"Kalaj","year":"2020","journal-title":"ACS Cent. Sci."},{"issue":"4","key":"2026081210073843000_cit3d","doi-asserted-by":"publisher","first-page":"2006291","DOI":"10.1002\/adfm.202006291","article-title":"Post-Synthetic\nModification of Metal\u2013Organic Frameworks Toward Applications","volume":"31","author":"Mandal","year":"2021","journal-title":"Adv. Funct. Mater."},{"issue":"2","key":"2026081210073843000_cit3e","doi-asserted-by":"publisher","first-page":"970","DOI":"10.1021\/cr200179u","article-title":"Postsynthetic Methods for the Functionalization\nof Metal\u2013Organic Frameworks","volume":"112","author":"Cohen","year":"2012","journal-title":"Chem. Rev."},{"issue":"45","key":"2026081210073843000_cit4","doi-asserted-by":"publisher","first-page":"24519","DOI":"10.1039\/D3TA05158G","article-title":"Post-synthesis modification of metal\u2013organic\nframeworks: synthesis, characteristics, and applications","volume":"11","author":"He","year":"2023","journal-title":"J. Mater. Chem. 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J."},{"key":"2026081210073843000_cit15b","doi-asserted-by":"publisher","first-page":"2055","DOI":"10.1039\/B516365J","article-title":"A scandium\ncoordination polymer constructed from trimeric octahedral building\nblocks and 2,5-dihydroxyterephthalate","volume":"35","author":"Dietzel","year":"2006","journal-title":"Dalton\nTrans."},{"issue":"1","key":"2026081210073843000_cit16","doi-asserted-by":"publisher","first-page":"322","DOI":"10.1016\/j.micromeso.2010.12.016","article-title":"Synthesis,\ncharacterisation and adsorption properties\nof microporous scandium carboxylates with rigid and flexible frameworks","volume":"142","author":"Mowat","year":"2011","journal-title":"Microporous Mesoporous Mater."},{"issue":"14","key":"2026081210073843000_cit17","doi-asserted-by":"publisher","first-page":"3937","DOI":"10.1039\/C1DT11729G","article-title":"A novel structural\nform of MIL-53\nobserved for the scandium analogue and its response to temperature\nvariation and CO2 adsorption","volume":"41","author":"Mowat","year":"2012","journal-title":"Dalton\nTrans."},{"issue":"3","key":"2026081210073843000_cit18","doi-asserted-by":"publisher","first-page":"606","DOI":"10.1039\/C2CY20577G","article-title":"Remarkable Lewis\nacid catalytic performance of the scandium trimesate metal organic\nframework MIL-100(Sc) for C\u2013C and C=N bond-forming reactions","volume":"3","author":"Mitchell","year":"2013","journal-title":"Catal. Sci. Technol."},{"key":"2026081210073843000_cit19a","doi-asserted-by":"publisher","first-page":"3850","DOI":"10.1039\/b506677h","article-title":"A microporous\nscandium terephthalate, Sc2(O2CC6H4CO2)3, with high thermal stability","volume":"41","author":"Miller","year":"2005","journal-title":"Chem. Commun."},{"issue":"23","key":"2026081210073843000_cit19b","doi-asserted-by":"publisher","first-page":"5837","DOI":"10.1021\/cm051362e","article-title":"Metal\u2013Organic\nScandium Framework: Useful Material for Hydrogen Storage and Catalysis","volume":"17","author":"Perles","year":"2005","journal-title":"Chem. Mater."},{"key":"2026081210073843000_cit20","doi-asserted-by":"publisher","first-page":"3377","DOI":"10.1039\/D1MH01663F","article-title":"Exploring and Expanding\nthe Fe-Terephthalate Metal-Organic\nFramework Phase Space by Coordination and Oxidation Modulation","volume":"8","author":"Bara","year":"2021","journal-title":"Mater. Horiz."},{"issue":"18","key":"2026081210073843000_cit21","doi-asserted-by":"publisher","first-page":"4546","DOI":"10.1039\/D0SC01356K","article-title":"Modulated\nself-assembly of metal\u2013organic frameworks","volume":"11","author":"Forgan","year":"2020","journal-title":"Chem. Sci."},{"issue":"3","key":"2026081210073843000_cit22","doi-asserted-by":"publisher","first-page":"659","DOI":"10.1021\/acs.accounts.7b00497","article-title":"Thermodynamic and Kinetic Effects\nin the Crystallization of Metal\u2013Organic Frameworks","volume":"51","author":"Cheetham","year":"2018","journal-title":"Acc. Chem. Res."},{"issue":"11","key":"2026081210073843000_cit23","doi-asserted-by":"publisher","first-page":"5036","DOI":"10.1021\/cg4012058","article-title":"Framework Isomerism\nin Vanadium Metal\u2013Organic\nFrameworks: MIL-88B(V) and MIL-101(V)","volume":"13","author":"Carson","year":"2013","journal-title":"Cryst.\nGrowth Des."},{"key":"2026081210073843000_cit24","doi-asserted-by":"publisher","first-page":"113868","DOI":"10.1016\/j.micromeso.2025.113868","article-title":"A multinuclear approach to characterising\ndisordered (Al,Sc)-MIL-53 using solid-state NMR spectroscopy","volume":"399","author":"Borthwick","year":"2026","journal-title":"Microporous Mesoporous Mater."},{"issue":"1","key":"2026081210073843000_cit25","doi-asserted-by":"publisher","first-page":"90","DOI":"10.1038\/s41557-019-0364-0","article-title":"Rapid\ndesolvation-triggered domino lattice rearrangement\nin a metal\u2013organic framework","volume":"12","author":"Lo","year":"2020","journal-title":"Nat. Chem."},{"issue":"20","key":"2026081210073843000_cit26a","doi-asserted-by":"publisher","first-page":"16766","DOI":"10.1021\/jacs.5c03967","article-title":"Zero-\nto One-Dimensional Transformation in a Highly Porous Metal\u2013Organic\nFramework to Enhance Physicochemical Properties","volume":"147","author":"Jiang","year":"2025","journal-title":"J. Am. Chem. Soc."},{"issue":"4","key":"2026081210073843000_cit26b","doi-asserted-by":"publisher","first-page":"1034","DOI":"10.1039\/B918269C","article-title":"Remarkable\nstructural diversity and single-crystal-to-single-crystal transformations\nin sulfone functionalized lanthanide MOFs","volume":"12","author":"Neofotistou","year":"2010","journal-title":"Cryst.\nEng. Comm."},{"issue":"7","key":"2026081210073843000_cit27","doi-asserted-by":"publisher","first-page":"3681","DOI":"10.1021\/acs.chemrev.7b00582","article-title":"In Situ,\nTime-Resolved, and Mechanistic Studies of Metal\u2013Organic Framework\nNucleation and Growth","volume":"118","author":"Van Vleet","year":"2018","journal-title":"Chem. Rev."},{"issue":"4","key":"2026081210073843000_cit28","doi-asserted-by":"publisher","first-page":"763","DOI":"10.1002\/anie.200905627","article-title":"Time-Resolved In Situ Diffraction\nStudy of the Solvothermal Crystallization of Some Prototypical Metal\u2013Organic\nFrameworks","volume":"49","author":"Millange","year":"2010","journal-title":"Angew. Chem., Int. Ed."},{"issue":"41","key":"2026081210073843000_cit29","doi-asserted-by":"publisher","first-page":"9624","DOI":"10.1002\/anie.201101757","article-title":"Kinetic Control\nof Metal\u2013Organic Framework Crystallization Investigated by\nTime-Resolved In Situ X-Ray Scattering","volume":"50","author":"Stavitski","year":"2011","journal-title":"Angew.\nChem., Int. Ed."},{"key":"2026081210073843000_cit30","doi-asserted-by":"publisher","first-page":"131","DOI":"10.1016\/j.micromeso.2011.08.016","article-title":"The progression of Al-based metal-organic\nframeworks\n\u2013 From academic research to industrial production and applications","volume":"157","author":"Gaab","year":"2012","journal-title":"Microporous Mesoporous Mater."},{"issue":"8","key":"2026081210073843000_cit31","doi-asserted-by":"publisher","first-page":"1330","DOI":"10.1016\/j.bbabio.2014.03.013","article-title":"Unsuspected task for\nan old team: succinate, fumarate and other Krebs cycle acids in metabolic\nremodeling","volume":"1837","author":"Be\u0301nit","year":"2014","journal-title":"Biochim. Biophys. 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