Muon spectroscopy of a 12-phosphatetraphene with extremely efficient radical trapping properties

Muon spectroscopy of a 12-phosphatetraphene with extremely efficient radical trapping properties | 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 Muon spectroscopy of a 12-phosphatetraphene with extremely efficient radical trapping properties Shigekazu Ito, Kohei Yasuda, Keisuke Ishihara, Victoria L. Karner, and 2 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4921365/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 07 Jan, 2025 Read the published version in Scientific Reports → Version 1 posted 10 You are reading this latest preprint version Abstract This paper describes muon spin spectroscopy (µSR) studies of 12-phosphatetraphene stabilized by a peri-trifluoromethyl group and a meso-aryl substituent. Even though the prepared solution in tetrahydrofuran (THF) was quite dilute (0.060 M) for transverse-field muon spin rotation (TF-µSR) measurements, the π-extended heavier congener of tetraphene presented a pair of signals due to a muoniated radical from which the muon hyperfine coupling constant (hfc) was determined. This muoniated radical was produced by the diffusion-controlled regioselective addition of muonium (Mu = [µ+e–]) to the sp2-type phosphorus atom. The assignment of the muoniated radical structure was confirmed by observing a resonance due to the I = 1/2 (31P) nucleus in a muon (avoided) level-crossing resonance (µLCR) spectrum. The 31P hfc was determined from the resonance position, and a comparison with the value obtained from density functional theory (DFT) calculations indicated that the radical retained a flat π-delocalized tetracyclic skeleton. This higher energy structure is hypothesized to be preferable because of the increased zero-point energy of the light mass of the muon. The findings of this study could be fruitful in the development of novel spin-functional materials featuring efficient radical capture and π-delocalized paramagnetic molecular systems. Physical sciences/Chemistry/Physical chemistry/Chemical physics Physical sciences/Chemistry/Theoretical chemistry/Density functional theory Muon Radicals Heterocycles Isotope effects Reaction kinetics DFT calculations Full Text Additional Declarations No competing interests reported. Supplementary Files SupportingInformation0806.pdf Cite Share Download PDF Status: Published Journal Publication published 07 Jan, 2025 Read the published version in Scientific Reports → Version 1 posted Editorial decision: Revision requested 30 Sep, 2024 Reviews received at journal 30 Sep, 2024 Reviews received at journal 06 Sep, 2024 Reviewers agreed at journal 02 Sep, 2024 Reviewers agreed at journal 02 Sep, 2024 Reviewers invited by journal 02 Sep, 2024 Editor assigned by journal 02 Sep, 2024 Editor invited by journal 31 Aug, 2024 Submission checks completed at journal 30 Aug, 2024 First submitted to journal 15 Aug, 2024 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-4921365","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":357501218,"identity":"6e5cdbff-cab1-4016-a9af-47bbb8a6b590","order_by":0,"name":"Shigekazu Ito","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA9ElEQVRIiWNgGAWjYBACNhiDH0QkALEBmMuDRwtMj2QDA2NDQgIRWuDWGBwAamGAa8ED+OSbDzD+YLCTM752gP3Bwx828uYMzA8/MMjcweMwtgRmHoZkY7PbCSCHpRnubGAzlmDgeYZHC48BMwMDc+I2iJbDCUAXmgH9chivFqDD6hM3zwZr+Q/Uwv6NoBZg8BxO3CAN1nIAqIWHkC1pCYd5DI4bS9xObJyRkJZsuOEwT7FEAh6/yDcfPvjwR0W1HP/s5AMff9jYyRscb9/44WMP7hADgQOQuABGCxgAQ4MhsecAXi3YwA/StYyCUTAKRsGwBQBBbksq1NTs5QAAAABJRU5ErkJggg==","orcid":"","institution":"Tokyo Institute of Technology","correspondingAuthor":true,"prefix":"","firstName":"Shigekazu","middleName":"","lastName":"Ito","suffix":""},{"id":357501219,"identity":"0cefac33-734e-4d15-b4fe-17900c8f8786","order_by":1,"name":"Kohei Yasuda","email":"","orcid":"","institution":"Tokyo Institute of Technology","correspondingAuthor":false,"prefix":"","firstName":"Kohei","middleName":"","lastName":"Yasuda","suffix":""},{"id":357501220,"identity":"f907f9e1-f0b1-4916-b135-8033376e5df1","order_by":2,"name":"Keisuke Ishihara","email":"","orcid":"","institution":"Tokyo Institute of Technology","correspondingAuthor":false,"prefix":"","firstName":"Keisuke","middleName":"","lastName":"Ishihara","suffix":""},{"id":357501221,"identity":"229a81cc-2b3d-43b5-bde4-3eb270a70dad","order_by":3,"name":"Victoria L. 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Even though the prepared solution in tetrahydrofuran (THF) was quite dilute (0.060 M) for transverse-field muon spin rotation (TF-µSR) measurements, the π-extended heavier congener of tetraphene presented a pair of signals due to a muoniated radical from which the muon hyperfine coupling constant (hfc) was determined. This muoniated radical was produced by the diffusion-controlled regioselective addition of muonium (Mu = [µ+e–]) to the sp2-type phosphorus atom. The assignment of the muoniated radical structure was confirmed by observing a resonance due to the I = 1/2 (31P) nucleus in a muon (avoided) level-crossing resonance (µLCR) spectrum. The 31P hfc was determined from the resonance position, and a comparison with the value obtained from density functional theory (DFT) calculations indicated that the radical retained a flat π-delocalized tetracyclic skeleton. This higher energy structure is hypothesized to be preferable because of the increased zero-point energy of the light mass of the muon. 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