Synthesis of micrometre-thick oriented 2D covalent organic framework films by a kinetic polymerization pathway

Synthesis of micrometre-thick oriented 2D covalent organic framework films by a kinetic polymerization pathway | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Synthesis of micrometre-thick oriented 2D covalent organic framework films by a kinetic polymerization pathway Luca Cusin, Piotr Cieciórski, Samuel Van Gele, Fabian Heck, Simon Krause, and 4 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-3943499/v4 This work is licensed under a CC BY 4.0 License Status: Posted Version 4 posted You are reading this latest preprint version Show more versions Abstract Despite advances in the field of 2D polymerization, the synthesis of high-quality, micron-thick films of oriented 2D covalent organic frameworks (COFs) remains challenging. Conventional approaches focusing on thermodynamic control of the polymerization pathway face a detrimental trade-off between orientation and thickness. In this study, we describe a straightforward method for preparing imine-linked 2D COF films with a near-perfect face-on orientation by leveraging kinetically-trapped amorphous 3D covalent adaptable network (CAN) intermediates. These off-pathway intermediates are generated as coatings through solution casting, during which the CANs spontaneously align to relax tensile stresses induced by solvent evaporation. A subsequent lift-off process, followed by an amorphous-to-crystalline transformation under solvothermal conditions, converts the 3D-oriented polymer networks into thermodynamically stable, porous, and free-standing 2D COF films. This versatile kinetic trapping strategy is suitable for a range of building blocks and network topologies, constituting a convenient synthetic tool for accessing high-quality, robust, large-area 2D COF films with a strongly aligned polycrystalline structure. Materials Chemistry non-equilibrium synthesis covalent adaptable networks covalent organic frameworks solventborne polymer films anisotropic materials porous materials stress relaxation Full Text Additional Declarations The authors declare no competing interests. Cite Share Download PDF Status: Posted Version 4 posted You are reading this latest preprint version Show more versions Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-3943499","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":295868527,"identity":"27a00497-49d4-4ef1-8cb9-d8830b63ecf1","order_by":0,"name":"Luca Cusin","email":"","orcid":"https://orcid.org/0000-0002-7845-0947","institution":"Université de Strasbourg, CNRS, ISIS UMR 7006","correspondingAuthor":false,"prefix":"","firstName":"Luca","middleName":"","lastName":"Cusin","suffix":""},{"id":295868528,"identity":"63e8c530-c09b-4330-9b47-ca5d7c2cdf5a","order_by":1,"name":"Piotr Cieciórski","email":"","orcid":"https://orcid.org/0000-0003-0507-1513","institution":"Faculty of Chemistry, University of Warsaw","correspondingAuthor":false,"prefix":"","firstName":"Piotr","middleName":"","lastName":"Cieciórski","suffix":""},{"id":295868529,"identity":"b442fbd7-f2c5-4759-a732-b05debb2f7f7","order_by":2,"name":"Samuel Van Gele","email":"","orcid":"https://orcid.org/0009-0003-9048-9451","institution":"Nanochemistry Department, Max Planck Institute for Solid State Research; Department of Chemistry, Ludwig Maximilians-Universität München","correspondingAuthor":false,"prefix":"","firstName":"Samuel","middleName":"Van","lastName":"Gele","suffix":""},{"id":295868530,"identity":"2a729506-2f03-42be-adfb-381f08fe0c32","order_by":3,"name":"Fabian Heck","email":"","orcid":"https://orcid.org/0000-0003-0198-3398","institution":"Nanochemistry Department, Max Planck Institute for Solid State Research; Department of Chemistry, Ludwig Maximilians-Universität München","correspondingAuthor":false,"prefix":"","firstName":"Fabian","middleName":"","lastName":"Heck","suffix":""},{"id":295868531,"identity":"5b05903a-3bd8-436d-9159-c94d11dc82d8","order_by":4,"name":"Simon Krause","email":"","orcid":"https://orcid.org/0000-0001-9504-8514","institution":"Nanochemistry Department, Max Planck Institute for Solid State Research","correspondingAuthor":false,"prefix":"","firstName":"Simon","middleName":"","lastName":"Krause","suffix":""},{"id":295868532,"identity":"98228598-1174-4cae-a3b1-c1f624192beb","order_by":5,"name":"Pawel W. Majewski","email":"","orcid":"https://orcid.org/0000-0001-6338-2411","institution":"Faculty of Chemistry, University of Warsaw","correspondingAuthor":false,"prefix":"","firstName":"Pawel","middleName":"W.","lastName":"Majewski","suffix":""},{"id":295868533,"identity":"9b8cf343-0f84-48ad-9dc1-a4a2802baa0f","order_by":6,"name":"Bettina V. Lotsch","email":"","orcid":"https://orcid.org/0000-0002-3094-303X","institution":"Nanochemistry Department, Max Planck Institute for Solid State Research; Department of Chemistry, Ludwig Maximilians-Universität München","correspondingAuthor":false,"prefix":"","firstName":"Bettina","middleName":"V.","lastName":"Lotsch","suffix":""},{"id":295868534,"identity":"e81663ff-830a-412e-854f-1ad677ef0ad0","order_by":7,"name":"Wojciech Danowski","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA1UlEQVRIie3OoQvCQBTH8RPhLE+tDgX/hScHS4r/ypPB0tNiMV6a0eqfc2PBoliXRLGu2CZMcCpYhJ02w33D3a98uBPC5frHzPMkaL933XxJPP3YVG5J3xGB5nXbSWuzi89QhD2VTuP4mh/6QjaPlcTbzgLVjBj8dEYJ0HygZQMrCRr2u1O9KAljIohquh9Vfwz3md/lYgFqzRjnRGMtpYWk5SssGbDDaIBoYiVemil1i0LobDNMIKQgspHWngendRGM20tWl3xIo5WNfPYzcLlcLtdnd/x4RCZQrsUoAAAAAElFTkSuQmCC","orcid":"https://orcid.org/0000-0002-8588-8912","institution":"Université de Strasbourg, CNRS, ISIS UMR 7006","correspondingAuthor":true,"prefix":"","firstName":"Wojciech","middleName":"","lastName":"Danowski","suffix":""},{"id":295868535,"identity":"9f87d00d-5655-4a0a-a294-8a456e9c1f00","order_by":8,"name":"Paolo Samorì","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAwElEQVRIiWNgGAWjYNACAxsGBmYIk59YLWkgLYwNQKZkA5F6DoMIIrXIt59OfFxRcD5xOzv788cVNQwS5oT0GJzJ3Wx4xuB24s5mHsPGM8cYJGQOENLCkLtNsgGoZcNhHsbGBjaGOgmCDut/C9JyDqiF/WFjwz8GCYJaGG6AbTkA1MJg2NjYRoQWgxtvNxs2GCQbAx1mOLOxT4KwFvn+3I0PG/7YyW44f/zBx4ZvNkQ4DA2QrGEUjIJRMApGATYAACxlPxAgxahHAAAAAElFTkSuQmCC","orcid":"https://orcid.org/0000-0001-6256-8281","institution":"Université de Strasbourg, CNRS, ISIS UMR 7006","correspondingAuthor":true,"prefix":"","firstName":"Paolo","middleName":"","lastName":"Samorì","suffix":""}],"badges":[],"createdAt":"2024-02-09 16:04:24","currentVersionCode":4,"declarations":{"humanSubjects":false,"vertebrateSubjects":false,"conflictsOfInterestStatement":false,"humanSubjectEthicalGuidelines":false,"humanSubjectConsent":false,"humanSubjectClinicalTrial":false,"humanSubjectCaseReport":false,"vertebrateSubjectEthicalGuidelines":false},"doi":"10.21203/rs.3.rs-3943499/v4","doiUrl":"https://doi.org/10.21203/rs.3.rs-3943499/v4","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":79787685,"identity":"dfe47ce6-99dc-4e0f-bb97-877886a19d54","added_by":"auto","created_at":"2025-04-02 17:14:17","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":970487,"visible":true,"origin":"","legend":"","description":"","filename":"Preprintversion.pdf","url":"https://assets-eu.researchsquare.com/files/rs-3943499/v4_covered_f87b5e4a-2ee5-4389-bc0c-a5feb3808788.pdf"}],"financialInterests":"The authors declare no competing interests.","formattedTitle":"\u003cp\u003eSynthesis of micrometre-thick oriented 2D covalent organic framework films by a kinetic polymerization pathway\u003c/p\u003e","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":true,"highlight":"","institution":"University of Strasbourg","isAcceptedByJournal":false,"isAuthorSuppliedPdf":true,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":true,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"non-equilibrium synthesis, covalent adaptable networks, covalent organic frameworks, solventborne polymer films, anisotropic materials, porous materials, stress relaxation","lastPublishedDoi":"10.21203/rs.3.rs-3943499/v4","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-3943499/v4","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eDespite advances in the field of 2D polymerization, the synthesis of high-quality, micron-thick films of oriented 2D covalent organic frameworks (COFs) remains challenging. Conventional approaches focusing on thermodynamic control of the polymerization pathway face a detrimental trade-off between orientation and thickness. In this study, we describe a straightforward method for preparing imine-linked 2D COF films with a near-perfect face-on orientation by leveraging kinetically-trapped amorphous 3D covalent adaptable network (CAN) intermediates. These off-pathway intermediates are generated as coatings through solution casting, during which the CANs spontaneously align to relax tensile stresses induced by solvent evaporation. A subsequent lift-off process, followed by an amorphous-to-crystalline transformation under solvothermal conditions, converts the 3D-oriented polymer networks into thermodynamically stable, porous, and free-standing 2D COF films. This versatile kinetic trapping strategy is suitable for a range of building blocks and network topologies, constituting a convenient synthetic tool for accessing high-quality, robust, large-area 2D COF films with a strongly aligned polycrystalline structure.\u003c/p\u003e","manuscriptTitle":"Synthesis of micrometre-thick oriented 2D covalent organic framework films by a kinetic polymerization pathway","msid":"","msnumber":"","nonDraftVersions":[{"code":4,"date":"2025-04-02 16:50:11","doi":"10.21203/rs.3.rs-3943499/v4","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}},{"code":3,"date":"2024-04-26 14:02:31","doi":"10.21203/rs.3.rs-3943499/v3","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}},{"code":2,"date":"2024-04-16 21:37:00","doi":"10.21203/rs.3.rs-3943499/v2","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}},{"code":1,"date":"2024-02-12 05:07:27","doi":"10.21203/rs.3.rs-3943499/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"7d32b070-16e5-4cb1-9d35-975362563f95","owner":[],"postedDate":"April 2nd, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":44722320,"name":"Materials Chemistry"}],"tags":[],"updatedAt":"2024-05-17T11:40:42+00:00","versionOfRecord":[],"versionCreatedAt":"2025-04-02 16:50:11","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v4","identity":"rs-3943499","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-3943499","identity":"rs-3943499","version":["v4"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}