Donor-acceptor Stenhouse Adducts with Three Orthogonally Controlled Intrisic Stationary States

Donor-acceptor Stenhouse Adducts with Three Orthogonally Controlled Intrisic Stationary States | 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 Donor-acceptor Stenhouse Adducts with Three Orthogonally Controlled Intrisic Stationary States Yongli Duan, Haiquan Zhao, GuoDong Xue, Ze Wang, Chaoyue Xiong, and 4 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-43551/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Photoresponsive molecules with more than two intrinsic stationary states are very Interesting. Here, we demonstrate a series of crown ether (CE) substituted donor-acceptor Stenhouse adducts (DASAs) that can be switched between three stationary states under orthogonal control of light and metal ions. DASA-CE molecules are self-assembled into 1:1 head-to-tail supramolecular structures to form di-linear states due to strong van der Waals interactions between electron-donating and -withdrawing moieties. Furthermore, treatment with metal ions (Na+ or K+) switches the di-linear back to the linear state, which is reversible after adding free crown ether. On the other hand, green light irradiation induces linear -to- cyclic isomerization of DASA-CE, while the photoisomerization from di-linear to cyclic state is inhibited. The reverse cyclic -to- linear isomerization can occur under heating in the dark. All in all, the orthogonal switching of DASA-CE between di-linear , linear and cyclic states enables the development of smart materials in environments with complex stimuli. Photonics/optics donor-acceptor Stenhouse adducts photoresponsive orthogonal isomerization supramolecular chemistry Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Full Text Additional Declarations There is NO Competing Interest. Supplementary Files SupportingInformation1.pdf Donor-acceptor Stenhouse Adducts with Three Orthogonally Controlled Intrisic Stationary States Cite Share Download PDF Status: Posted 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-43551","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":917133,"identity":"ebdb68a1-4875-417b-a1d1-542416225449","order_by":0,"name":"Yongli Duan","email":"","orcid":"","institution":"University of Electronic Science and Technology of China","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Yongli","middleName":"","lastName":"Duan","suffix":""},{"id":917134,"identity":"fbc6915f-46c3-4c6a-b3d4-39906d79cd02","order_by":1,"name":"Haiquan Zhao","email":"","orcid":"","institution":"University of Electronic Science and Technology of China","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Haiquan","middleName":"","lastName":"Zhao","suffix":""},{"id":917135,"identity":"7965cdf8-3975-4110-afc5-0b409015709b","order_by":2,"name":"GuoDong Xue","email":"","orcid":"","institution":"University of Electronic Science and Technology of China","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"GuoDong","middleName":"","lastName":"Xue","suffix":""},{"id":917136,"identity":"666e0b94-e6aa-4ec5-b9cf-e0ca5af4bbc2","order_by":3,"name":"Ze Wang","email":"","orcid":"","institution":"Nanjing Tech University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Ze","middleName":"","lastName":"Wang","suffix":""},{"id":917137,"identity":"7c66da16-fd7c-4ba7-8f55-12e76c402317","order_by":4,"name":"Chaoyue Xiong","email":"","orcid":"","institution":"University of Electronic Science and Technology of China","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Chaoyue","middleName":"","lastName":"Xiong","suffix":""},{"id":917138,"identity":"00be2eb0-2358-4ab1-b4a8-5e4c7250c1d4","order_by":5,"name":"Lijun Mao","email":"","orcid":"","institution":"University of Electronic Science and Technology of China","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Lijun","middleName":"","lastName":"Mao","suffix":""},{"id":917139,"identity":"9ffbaf9d-aa0d-4ce9-afe2-5d0932803630","order_by":6,"name":"Chao He","email":"","orcid":"","institution":"Sichuan University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Chao","middleName":"","lastName":"He","suffix":""},{"id":917140,"identity":"206a8ec1-3eeb-4537-9cd8-3bed49dc1484","order_by":7,"name":"Dongsheng Wang","email":"","orcid":"","institution":"University of Electronic Science and Technology of China","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Dongsheng","middleName":"","lastName":"Wang","suffix":""},{"id":917141,"identity":"7d297a88-70f6-4ad2-9837-8b826820b300","order_by":8,"name":"Yonghao Zheng","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAABC0lEQVRIiWNgGAWjYDACCWTGBxiHh1gtjDNgqonWwsxDjBb52c3HHn5ts8mTj25++Ni2zcbenv0A44O3bQzy5ji0MM45lm4s25ZWbHjnmLFxbltaYg9PArPh3DYGw50N2LUwS+SYSUu2HU7cOCPBTDq37XACjwQDmzRvG0OCwQHsWtgk8r9BtaR/k7Zs+28P1ML+G58WHokcNsmPQC3zQdYxth1g7AHawoxPi4REmpk0w7m0xA0SOcWGPeeSE3vOJDZLzjknYbgBhxb5GcnPJH+U2STOn5G+8cGPMjt79vbDBz+8KbORx2ULOAh42RgYkBQwNjAgxRdWwPjjD9C6BrxqRsEoGAWjYCQDAEwwVd1qjkF+AAAAAElFTkSuQmCC","orcid":"https://orcid.org/0000-0003-1931-3536","institution":"University of Electronic Science and Technology of China","correspondingAuthor":true,"submittingAuthor":false,"prefix":"","firstName":"Yonghao","middleName":"","lastName":"Zheng","suffix":""}],"badges":[],"createdAt":"2020-07-15 10:45:51","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-43551/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-43551/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":1705366,"identity":"30b001d6-7da7-4dda-b8da-0e684b42d00e","added_by":"auto","created_at":"2020-07-28 14:01:59","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":123796,"visible":true,"origin":"","legend":"(a) UV/vis spectra of linear DASA-N (black, dot) and DASA-NC5 before (red, solid) and after (blue, solid) adding NaBF4 ([DASA-NC5] = [NaBF4] = 0.12 mM in THF). The inset shows the color change after adding NaBF4; (b) Absorbance variation at 560 (red) and 272 nm (blue) for DASA-NC5 with different concentrations after adding NaBF4 solution; (c) 1H NMR spectra (400 MHz at 298 K) of DASA-NC5 before (red) and after (blue) adding NaBF4 ([DASA-NC5] = 3 mM in THF-d8). (a, b, c…(black) represent the protons in linear DASA-NC5, a`, b`, c`…(blue) represent the protons in di-linear DASA-NC5).","description":"","filename":"Fig1.png","url":"https://assets-eu.researchsquare.com/files/rs-43551/v1/Fig1.png"},{"id":1705367,"identity":"715acd30-3904-4a32-8239-9579933f9f22","added_by":"auto","created_at":"2020-07-28 14:01:59","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":558372,"visible":true,"origin":"","legend":"(a) Calculated electrostatic potential distributions of linear and cyclic DASA-NC5; (b) Calculated molecular structure of linear DASA-NC5; (c) 1H,1H NOESY spectrum (400 MHz at 298 K) of DASA-NC5 before adding NaBF4 ([DASA-NC5] = 6 mM in THF-d8).","description":"","filename":"Fig2.png","url":"https://assets-eu.researchsquare.com/files/rs-43551/v1/Fig2.png"},{"id":1705368,"identity":"8bafe024-d02c-4b1f-ae3b-9ea4366d3784","added_by":"auto","created_at":"2020-07-28 14:01:59","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":483548,"visible":true,"origin":"","legend":"(a) Schematic illustration of the reversible transition of DASA-NC5 between the linear and di-linear states; (b) UV/vis spectra of DASA-NC5 before and after sequential treatment with NaBF4 and 15-crown-5 ([DASA-NC5] = [NaBF4] = 0.12 mM in THF). The inset shows the UV light region in detail; (c) Variation of absorbance at 560 nm of DASA-NC5 after repeaded treatment with NaBF4 and 15-crown-5 ([DASA-NC5] = 0.12 mM in THF; the amount of NaBF4 and 15-crown-5 added are kept the same for each cycle (in molar ratio)).","description":"","filename":"Fig3.png","url":"https://assets-eu.researchsquare.com/files/rs-43551/v1/Fig3.png"},{"id":1705369,"identity":"a1f50cc7-25e2-42ec-9273-8539bbcc4d30","added_by":"auto","created_at":"2020-07-28 14:01:59","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":478300,"visible":true,"origin":"","legend":"(a) Schematic illustration of light-induced isomerization between linear, di-linear and cyclic DASA-NC5; (b) UV/vis spectra of DASA-NC5 under dark (solid) and visible light irradiation (dot) before (black) and after (red) NaBF4 addition ([DASA-NC5] = 0.12 mM in THF); (c) 1H NMR spectra (400 MHz at 298 K) of DASA-NC5 under dark and visible light irradiation before NaBF4 addition ([DASA-NC5] = 3 mM in THF-d8). (a, b, c…(red) represent the protons in cyclic DASA-NC5)","description":"","filename":"Fig4.png","url":"https://assets-eu.researchsquare.com/files/rs-43551/v1/Fig4.png"},{"id":1705370,"identity":"5a73dbb3-a900-4424-b316-f4b655523084","added_by":"auto","created_at":"2020-07-28 14:01:59","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":176767,"visible":true,"origin":"","legend":"Scheme 1. Schematic illustration of orthogonal isomerization of DASA-CE under controlling of light and metal ions.","description":"","filename":"Scheme1.png","url":"https://assets-eu.researchsquare.com/files/rs-43551/v1/Scheme1.png"},{"id":13518232,"identity":"cdd1c304-ae7e-4c31-bd52-84fc35f746af","added_by":"auto","created_at":"2021-09-17 00:19:07","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1093517,"visible":true,"origin":"","legend":"Article File","description":"","filename":"1manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-43551/v1_covered.pdf"},{"id":1705373,"identity":"7a4eb33a-1908-47ba-a933-cec2a9f59cd2","added_by":"auto","created_at":"2020-07-28 14:02:03","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":797356,"visible":true,"origin":"","legend":"Article File","description":"","filename":"1manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-43551/v1_stamped.pdf"},{"id":1705371,"identity":"73a18747-bf87-44f6-919f-affe990e827e","added_by":"auto","created_at":"2020-07-28 14:02:00","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":766138,"visible":true,"origin":"","legend":"Article File","description":"","filename":"1manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-43551/v1/1manuscript.pdf"},{"id":1705372,"identity":"aa8cd13e-0b85-4beb-9a96-dc91705e2311","added_by":"auto","created_at":"2020-07-28 14:02:00","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":1822647,"visible":true,"origin":"","legend":"Donor-acceptor Stenhouse Adducts with Three Orthogonally Controlled Intrisic Stationary States","description":"","filename":"SupportingInformation1.pdf","url":"https://assets-eu.researchsquare.com/files/rs-43551/v1/SupportingInformation1.pdf"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Donor-acceptor Stenhouse Adducts with Three Orthogonally Controlled Intrisic Stationary States","fulltext":[{"header":"Full Text","content":"\u003cp\u003eThis preprint is available for \u003ca href='/article/rs-43551/latest.pdf' target='_blank'\u003edownload as a PDF\u003c/a\u003e.\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":true,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"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":"donor-acceptor Stenhouse adducts, photoresponsive, orthogonal, isomerization, supramolecular chemistry","lastPublishedDoi":"10.21203/rs.3.rs-43551/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-43551/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003ePhotoresponsive molecules with more than two intrinsic stationary states are very Interesting. Here, we demonstrate a series of crown ether (CE) substituted donor-acceptor Stenhouse adducts (DASAs) that can be switched between three stationary states under orthogonal control of light and metal ions. DASA-CE molecules are self-assembled into 1:1 head-to-tail supramolecular structures to form \u003cem\u003edi-linear\u003c/em\u003e states due to strong van der Waals interactions between electron-donating and -withdrawing moieties. Furthermore, treatment with metal ions (Na+ or K+) switches the \u003cem\u003edi-linear \u003c/em\u003eback to the \u003cem\u003elinear \u003c/em\u003estate, which is reversible after adding free crown ether. On the other hand, green light irradiation induces \u003cem\u003elinear\u003c/em\u003e-to-\u003cem\u003ecyclic \u003c/em\u003eisomerization of DASA-CE, while the photoisomerization from \u003cem\u003edi-linear\u003c/em\u003e to \u003cem\u003ecyclic \u003c/em\u003estate is inhibited. The reverse \u003cem\u003ecyclic\u003c/em\u003e-to-\u003cem\u003elinear \u003c/em\u003eisomerization can occur under heating in the dark. All in all, the orthogonal switching of DASA-CE between \u003cem\u003edi-linear\u003c/em\u003e, \u003cem\u003elinear \u003c/em\u003eand \u003cem\u003ecyclic \u003c/em\u003estates enables the development of smart materials in environments with complex stimuli.\u003c/p\u003e","manuscriptTitle":"Donor-acceptor Stenhouse Adducts with Three Orthogonally Controlled Intrisic Stationary States","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2020-07-28 14:01:58","doi":"10.21203/rs.3.rs-43551/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":"3fca835c-bed0-4371-9e0a-f7b108169545","owner":[],"postedDate":"July 28th, 2020","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":211200,"name":"Photonics/optics"}],"tags":[],"updatedAt":"2020-12-29T10:42:34+00:00","versionOfRecord":[],"versionCreatedAt":"2020-07-28 14:01:58","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-43551","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-43551","identity":"rs-43551","version":["v1"]},"buildId":"7rjqhiLT3MXkJMwkYKINL","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}