Breaking the Stability Barrier of Large Acenes

Breaking the Stability Barrier of Large Acenes | 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 Article Breaking the Stability Barrier of Large Acenes Yuming Zhao, Monther Zreid, Kaijie Ni, Jian-bin Lin This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6397479/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted You are reading this latest preprint version Abstract The synthesis and stabilization of large acenes have long been impeded by their inherent instability, which has limited their potential in electronic and magnetic applications. In this study, we present a breakthrough in the solution-phase synthesis of unprecedentedly stable long acenes, specifically [11]acenes and [13]acenes. This achievement was realized through a para-quinodimethane (p-QDM)-based design strategy combined with bulky trialkylsilylethynyl substitution, a method that surpasses all previously reported approaches for stabilizing large acenes. Comprehensive structural and spectroscopic characterization, including X-ray crystallography, UV–vis-NIR spectroscopy, electrochemical analysis, and EPR spectroscopy, confirmed the successful synthesis of these acenes. The results revealed that these large acenes exhibit significant open-shell biradical character in their ground states, accompanied by small singlet-to-triplet energy gaps. Their unique electronic and magnetic properties were further elucidated through magnetic measurements supported by density functional theory (DFT) calculations. This work represents a significant progress toward overcoming the long-standing challenge of stabilizing large acenes, opening new avenues for their exploration and integration into functional materials and device applications. Physical sciences/Chemistry/Organic chemistry/Synthetic chemistry methodology Physical sciences/Nanoscience and technology/Nanoscale materials/Electronic properties and materials acenes p-quinodimethane polycyclic aromatic compounds organic radicals Full Text Additional Declarations There is NO Competing Interest. Supplementary Files Supplementary.pdf Supplementary Information Cite Share Download PDF Status: Under Review Version 1 posted You are reading this latest preprint version 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. 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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-6397479","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":440206847,"identity":"7b0d9c18-76c2-4305-bff9-496356e1adeb","order_by":0,"name":"Yuming Zhao","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAm0lEQVRIiWNgGAWjYJCCAwwMNqRrSSPdosMkqDW4kZ14uODX+WiD2w2MH34QpyV3w+GZfbdzN9w5wCzZQ7QW3h6glhsJbAw8JGg5B9bC+IdoLTw/DoC1MBNli+SZt0BbGpJzZ95IbJaWIUYL3/HczZ95/tjl9t1IPvjxDTFaFA4ACcY2EJOxgRgNDAzyYHVEeXsUjIJRMApGLAAA0cM9A5dJCckAAAAASUVORK5CYII=","orcid":"https://orcid.org/0000-0002-1300-9309","institution":"Memorial University","correspondingAuthor":true,"prefix":"","firstName":"Yuming","middleName":"","lastName":"Zhao","suffix":""},{"id":440206848,"identity":"66708195-c4c1-4990-8f48-f28a72e895f5","order_by":1,"name":"Monther Zreid","email":"","orcid":"","institution":"Memorial University","correspondingAuthor":false,"prefix":"","firstName":"Monther","middleName":"","lastName":"Zreid","suffix":""},{"id":440206849,"identity":"64634cf8-d1a3-4e14-bb22-b9bd858320a7","order_by":2,"name":"Kaijie Ni","email":"","orcid":"","institution":"College of Chemistry and Materials Engineering, Zhejiang Agriculture \u0026 Forestry University","correspondingAuthor":false,"prefix":"","firstName":"Kaijie","middleName":"","lastName":"Ni","suffix":""},{"id":440206850,"identity":"8f19a112-b547-46a4-9a45-b26f1819e0bd","order_by":3,"name":"Jian-bin Lin","email":"","orcid":"","institution":"Memorial University","correspondingAuthor":false,"prefix":"","firstName":"Jian-bin","middleName":"","lastName":"Lin","suffix":""}],"badges":[],"createdAt":"2025-04-07 21:50:25","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6397479/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6397479/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":81385669,"identity":"be358fc9-476d-4b98-abc2-09caab916418","added_by":"auto","created_at":"2025-04-25 13:38:46","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":5658070,"visible":true,"origin":"","legend":"Article File","description":"","filename":"ManuscriptVer1.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6397479/v1_covered_7c356eb2-837b-4dee-a7b6-03c27e9b54f7.pdf"},{"id":80687142,"identity":"1b074561-80a3-4329-bde5-36f7514a4b3f","added_by":"auto","created_at":"2025-04-16 04:01:03","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":49896071,"visible":true,"origin":"","legend":"Supplementary Information","description":"","filename":"Supplementary.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6397479/v1/fa4a93a482c0c67a21b496c3.pdf"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Breaking the Stability Barrier of Large Acenes","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":true,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":true,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"acenes, p-quinodimethane, polycyclic aromatic compounds, organic radicals","lastPublishedDoi":"10.21203/rs.3.rs-6397479/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6397479/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"The synthesis and stabilization of large acenes have long been impeded by\r\ntheir inherent instability, which has limited their potential in electronic and\r\nmagnetic applications. In this study, we present a breakthrough in the solution-phase\r\nsynthesis of unprecedentedly stable long acenes, specifically [11]acenes\r\nand [13]acenes. This achievement was realized through a para-quinodimethane\r\n(p-QDM)-based design strategy combined with bulky trialkylsilylethynyl substitution,\r\na method that surpasses all previously reported approaches for stabilizing\r\nlarge acenes. Comprehensive structural and spectroscopic characterization,\r\nincluding X-ray crystallography, UV–vis-NIR spectroscopy, electrochemical analysis,\r\nand EPR spectroscopy, confirmed the successful synthesis of these acenes.\r\nThe results revealed that these large acenes exhibit significant open-shell biradical\r\ncharacter in their ground states, accompanied by small singlet-to-triplet energy\r\ngaps. Their unique electronic and magnetic properties were further elucidated\r\nthrough magnetic measurements supported by density functional theory (DFT)\r\ncalculations. This work represents a significant progress toward overcoming the\r\nlong-standing challenge of stabilizing large acenes, opening new avenues for their\r\nexploration and integration into functional materials and device applications.","manuscriptTitle":"Breaking the Stability Barrier of Large Acenes","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-04-16 04:00:58","doi":"10.21203/rs.3.rs-6397479/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"nature-communications","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"NCOMMS","sideBox":"Learn more about [Nature Communications](http://www.nature.com/ncomms/)","snPcode":"","submissionUrl":"https://mts-ncomms.nature.com/","title":"Nature Communications","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature Communications","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"b2f62bc8-0eaf-4b6f-988a-7b757743f570","owner":[],"postedDate":"April 16th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[{"id":46866129,"name":"Physical sciences/Chemistry/Organic chemistry/Synthetic chemistry methodology"},{"id":46866130,"name":"Physical sciences/Nanoscience and technology/Nanoscale materials/Electronic properties and materials"}],"tags":[],"updatedAt":"2025-05-05T19:46:09+00:00","versionOfRecord":[],"versionCreatedAt":"2025-04-16 04:00:58","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-6397479","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6397479","identity":"rs-6397479","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}