Spin-Canted Mn–Mn Coupling in Symmetry-Broken Chloride Dimer with Dual-Responsive Luminescence and Sensing

Spin-Canted Mn–Mn Coupling in Symmetry-Broken Chloride Dimer with Dual-Responsive Luminescence and Sensing | 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 Spin-Canted Mn–Mn Coupling in Symmetry-Broken Chloride Dimer with Dual-Responsive Luminescence and Sensing Jianwei Qiao, Guojun Zhou, Pei Wang, Qiqiong Ren, Nan Zhang, Jin Lv, and 2 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7666204/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 28 Jan, 2026 Read the published version in Light: Science & Applications → Version 1 posted 15 You are reading this latest preprint version Abstract Magneto-optical coupling offers a potent alternative to crystal field engineering for tailoring Mn 2+ luminescence. However, precise control over Mn–Mn coupling is hindered by complex spin-electron super-exchange interactions. Here, we report a symmetry-broken Mn(II) chloride dimer, (C 10 H 20 O 5 Mn)(CH 3 CN)MnCl 4 , synthesized via a crown-ether-assisted supramolecular strategy. The dimer feathers a 7-coordinated pentagonal bipyramid and a 4-coordinated tetrahedron linked by a distorted Mn–Cl–Mn bridge (129°), which promotes unprecedented spin-canted Mn–Mn coupling and creates a novel Mn–Mn luminescent center. This center exhibits a red emission at 638 nm with an unusually short lifetime of 0.42 ms, attributed to the relaxation of the spin-forbidden d – d transitions. Remarkably, the emission undergoes a 30 nm blue-shift upon heating (5-305 K) due to the thermal suppression of spin-canting, and a 40 nm blue-shift under pressure (0-20 MPa) through reduced orbital overlap. This dual-responsive luminescence originates from spin-canted weak ferromagnetism, which rearranges energy-levels by separating antibonding orbitals. Using this effect, we develop an optical manometer for real-time underwater depth sensing. These findings highlight spin-canted Mn(II) dimers as a promising platform for stimuli-responsive luminescence and a new mechanism for d–d transition modulation. Physical sciences/Optics and photonics/Optical physics/Micro-optics Physical sciences/Optics and photonics/Optical materials and structures/Photonic crystals Full Text Additional Declarations There is no conflict of interest Supplementary Files checkcif.pdf checkCIF/PLATON report C12H23Cl4Mn2NO5.cif The crystallographic information file (CIF) SupplementaryInformation.docx Supplementary Information Cite Share Download PDF Status: Published Journal Publication published 28 Jan, 2026 Read the published version in Light: Science & Applications → Version 1 posted Editorial decision: revise 16 Oct, 2025 Review # 5 received at journal 09 Oct, 2025 Review # 4 received at journal 05 Oct, 2025 Review # 2 received at journal 30 Sep, 2025 Review # 1 received at journal 30 Sep, 2025 Review # 3 received at journal 28 Sep, 2025 Reviewer # 5 agreed at journal 28 Sep, 2025 Reviewer # 4 agreed at journal 25 Sep, 2025 Reviewer # 3 agreed at journal 24 Sep, 2025 Reviewer # 2 agreed at journal 24 Sep, 2025 Reviewer # 1 agreed at journal 24 Sep, 2025 Reviewers invited by journal 24 Sep, 2025 Submission checks completed at journal 22 Sep, 2025 Editor assigned by journal 20 Sep, 2025 First submitted to journal 20 Sep, 2025 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. 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-7666204","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":519776136,"identity":"86e6ecd9-b179-4b09-b6b0-445b31a1e259","order_by":0,"name":"Jianwei 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Sensing","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":true,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":true,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"light-science-and-applications","isNatureJournal":false,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"lsa","sideBox":"Learn more about [Light: Science \u0026 Applications](http://www.nature.com/lsa/)","snPcode":"41377","submissionUrl":"https://mts-lsa.nature.com/","title":"Light: Science \u0026 Applications","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature AJ","inReviewEnabled":true,"inReviewRevisionsEnabled":true},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-7666204/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-7666204/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eMagneto-optical coupling offers a potent alternative to crystal field engineering for tailoring Mn\u003csup\u003e2+\u003c/sup\u003e luminescence. However, precise control over Mn–Mn coupling is hindered by complex spin-electron super-exchange interactions. Here, we report a symmetry-broken Mn(II) chloride dimer, (C\u003csub\u003e10\u003c/sub\u003eH\u003csub\u003e20\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003eMn)(CH\u003csub\u003e3\u003c/sub\u003eCN)MnCl\u003csub\u003e4\u003c/sub\u003e, synthesized via a crown-ether-assisted supramolecular strategy. The dimer feathers a 7-coordinated pentagonal bipyramid and a 4-coordinated tetrahedron linked by a distorted Mn–Cl–Mn bridge (129°), which promotes unprecedented spin-canted Mn–Mn coupling and creates a novel Mn–Mn luminescent center. This center exhibits a red emission at 638 nm with an unusually short lifetime of 0.42 ms, attributed to the relaxation of the spin-forbidden \u003cem\u003ed\u003c/em\u003e–\u003cem\u003ed\u003c/em\u003e transitions. Remarkably, the emission undergoes a 30 nm blue-shift upon heating (5-305 K) due to the thermal suppression of spin-canting, and a 40 nm blue-shift under pressure (0-20 MPa) through reduced orbital overlap. This dual-responsive luminescence originates from spin-canted weak ferromagnetism, which rearranges energy-levels by separating antibonding orbitals. Using this effect, we develop an optical manometer for real-time underwater depth sensing. These findings highlight spin-canted Mn(II) dimers as a promising platform for stimuli-responsive luminescence and a new mechanism for \u003cem\u003ed–d\u003c/em\u003e transition modulation.\u003c/p\u003e","manuscriptTitle":"Spin-Canted Mn–Mn Coupling in Symmetry-Broken Chloride Dimer with Dual-Responsive Luminescence and Sensing","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-10-07 18:57:52","doi":"10.21203/rs.3.rs-7666204/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"revise","date":"2025-10-16T09:09:14+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"This content is not available.","date":"2025-10-09T13:09:39+00:00","index":5,"fulltext":"This content is not available."},{"type":"editorInvitedReview","content":"This content is not available.","date":"2025-10-05T14:13:14+00:00","index":4,"fulltext":"This content is not available."},{"type":"editorInvitedReview","content":"This content is not available.","date":"2025-09-30T15:55:55+00:00","index":2,"fulltext":"This content is not available."},{"type":"editorInvitedReview","content":"This content is not available.","date":"2025-09-30T10:06:24+00:00","index":1,"fulltext":"This content is not available."},{"type":"editorInvitedReview","content":"This content is not available.","date":"2025-09-28T17:40:32+00:00","index":3,"fulltext":"This content is not available."},{"type":"reviewerAgreed","content":"This content is not available.","date":"2025-09-28T07:21:24+00:00","index":5,"fulltext":"This content is not available."},{"type":"reviewerAgreed","content":"This content is not available.","date":"2025-09-25T07:53:55+00:00","index":4,"fulltext":"This content is not available."},{"type":"reviewerAgreed","content":"This content is not available.","date":"2025-09-25T00:42:27+00:00","index":3,"fulltext":"This content is not available."},{"type":"reviewerAgreed","content":"This content is not available.","date":"2025-09-24T14:29:37+00:00","index":2,"fulltext":"This content is not available."},{"type":"reviewerAgreed","content":"This content is not available.","date":"2025-09-24T08:14:03+00:00","index":1,"fulltext":"This content is not available."},{"type":"reviewersInvited","content":"","date":"2025-09-24T06:46:30+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-09-23T02:24:19+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-09-21T02:57:04+00:00","index":"","fulltext":""},{"type":"submitted","content":"Light: Science \u0026 Applications","date":"2025-09-21T02:57:03+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"light-science-and-applications","isNatureJournal":false,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"lsa","sideBox":"Learn more about [Light: Science \u0026 Applications](http://www.nature.com/lsa/)","snPcode":"41377","submissionUrl":"https://mts-lsa.nature.com/","title":"Light: Science \u0026 Applications","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature AJ","inReviewEnabled":true,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"177c610a-2b40-460b-af33-c7a83d66eeab","owner":[],"postedDate":"October 7th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":55240501,"name":"Physical sciences/Optics and photonics/Optical physics/Micro-optics"},{"id":55240502,"name":"Physical sciences/Optics and photonics/Optical materials and structures/Photonic crystals"}],"tags":[],"updatedAt":"2026-01-29T08:25:45+00:00","versionOfRecord":{"articleIdentity":"rs-7666204","link":"https://doi.org/10.1038/s41377-025-02154-9","journal":{"identity":"light-science-and-applications","isVorOnly":false,"title":"Light: Science \u0026 Applications"},"publishedOn":"2026-01-28 05:00:00","publishedOnDateReadable":"January 28th, 2026"},"versionCreatedAt":"2025-10-07 18:57:52","video":"","vorDoi":"10.1038/s41377-025-02154-9","vorDoiUrl":"https://doi.org/10.1038/s41377-025-02154-9","workflowStages":[]},"version":"v1","identity":"rs-7666204","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7666204","identity":"rs-7666204","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}