Reversible conformational change coupled electron transfer (CCET) for stable redox-active molecules

Reversible conformational change coupled electron transfer (CCET) for stable redox-active molecules | 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 Reversible conformational change coupled electron transfer (CCET) for stable redox-active molecules Christian Malapit, An Kitamura, Jake Evans This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6835054/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 Reversible electron transfer is a fundamental process that is essential in redox-active organic molecules and materials (ROMs) across biological, chemical, and energy technologies. Achieving stable and reversible redox behavior often requires careful molecular design or coupling electron transfer with a chemical step, such as proton-coupled electron transfer (PCET). In this study, we investigate a distinct stabilization mechanism based on conformational change coupled electron transfer (CCET). We show that acyclic 1,2-dicarbonyl compounds exhibit enhanced electrochemical stability by undergoing a conformational shift from skewed cis-geometries to more stable trans-conformations upon reduction, enabling stability even at more negative reduction potentials. Mechanistic studies demonstrate that CCET stabilizes the reduced state by allowing bond rotation that minimizes electron repulsion and delocalizes electron density by retaining a trans-planar geometry. Unlike PCET, which shifts reduction potentials positively, CCET enhances stability even at more negative potentials—breaking the conventional trade-off between redox potential and stability. Charge-discharge cycling of benzil shows 99.8% capacity retention over 500 cycles, demonstrating CCET as a powerful strategy for developing stable, high-performance ROMs for potential energy storage applications. Physical sciences/Chemistry/Organic chemistry/Reaction mechanisms Physical sciences/Chemistry/Electrochemistry/Electrocatalysis Physical sciences/Chemistry/Energy Full Text Additional Declarations There is NO Competing Interest. Supplementary Files CCETSI.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. We do this by developing innovative software and high quality services for the global research community. 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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-6835054","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":469946548,"identity":"7009e7e9-6814-47d0-9b25-a69e31f58d9c","order_by":0,"name":"Christian Malapit","email":"data:image/png;base64,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","orcid":"https://orcid.org/0000-0002-8471-4208","institution":"Northwestern University","correspondingAuthor":true,"prefix":"","firstName":"Christian","middleName":"","lastName":"Malapit","suffix":""},{"id":469946549,"identity":"43f4db13-ca7c-4f9e-9c1a-4bbacf594e4a","order_by":1,"name":"An Kitamura","email":"","orcid":"","institution":"Northwestern University","correspondingAuthor":false,"prefix":"","firstName":"An","middleName":"","lastName":"Kitamura","suffix":""},{"id":469946550,"identity":"3a410ba9-f6f2-49d5-80f5-fdf268eaad4b","order_by":2,"name":"Jake Evans","email":"","orcid":"","institution":"Northwestern University","correspondingAuthor":false,"prefix":"","firstName":"Jake","middleName":"","lastName":"Evans","suffix":""}],"badges":[],"createdAt":"2025-06-06 08:15:12","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6835054/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6835054/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":87440312,"identity":"ccdf84cf-d120-4cd1-a08d-8f9af9d76327","added_by":"auto","created_at":"2025-07-23 19:38:47","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1423058,"visible":true,"origin":"","legend":"Article File","description":"","filename":"CCETManuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6835054/v1_covered_6ccb3ec9-ded8-46c0-aa61-e66e4c339cab.pdf"},{"id":84464998,"identity":"32af76da-9864-4157-95e2-9ef5c6b193f7","added_by":"auto","created_at":"2025-06-12 09:36:42","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":6068694,"visible":true,"origin":"","legend":"Supplementary information","description":"","filename":"CCETSI.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6835054/v1/41ce20bd3575e4d678611a8e.pdf"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Reversible conformational change coupled electron transfer (CCET) for stable redox-active molecules","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":"","lastPublishedDoi":"10.21203/rs.3.rs-6835054/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6835054/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"Reversible electron transfer is a fundamental process that is essential in redox-active organic molecules and materials (ROMs) across biological, chemical, and energy technologies. 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