Muon spectroscopy of a 12-phosphatetraphene with extremely efficient radical trapping properties
Abstract This paper describes muon spin spectroscopy 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) measurem...
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Nature Portfolio
2025-01-01
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| Online Access: | https://doi.org/10.1038/s41598-024-84611-w |
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| author | Shigekazu Ito Kohei Yasuda Keisuke Ishihara Victoria L. Karner Kenji M. Kojima Iain McKenzie |
| author_facet | Shigekazu Ito Kohei Yasuda Keisuke Ishihara Victoria L. Karner Kenji M. Kojima Iain McKenzie |
| author_sort | Shigekazu Ito |
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| description | Abstract This paper describes muon spin spectroscopy 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-hybridized 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 developing novel spin-functional materials featuring efficient radical capture and π-delocalized paramagnetic molecular systems. |
| format | Article |
| id | doaj-art-d00804ffcbd6437b866ebb8665d664af |
| institution | Kabale University |
| issn | 2045-2322 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Nature Portfolio |
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| spelling | doaj-art-d00804ffcbd6437b866ebb8665d664af2025-01-12T12:18:55ZengNature PortfolioScientific Reports2045-23222025-01-0115111110.1038/s41598-024-84611-wMuon spectroscopy of a 12-phosphatetraphene with extremely efficient radical trapping propertiesShigekazu Ito0Kohei Yasuda1Keisuke Ishihara2Victoria L. Karner3Kenji M. Kojima4Iain McKenzie5Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of TechnologyDepartment of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of TechnologyDepartment of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of TechnologyCentre for Molecular and Materials Science, TRIUMFCentre for Molecular and Materials Science, TRIUMFCentre for Molecular and Materials Science, TRIUMFAbstract This paper describes muon spin spectroscopy 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-hybridized 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 developing novel spin-functional materials featuring efficient radical capture and π-delocalized paramagnetic molecular systems.https://doi.org/10.1038/s41598-024-84611-wMuonRadicalsHeterocyclesIsotope effectsReaction kineticsDFT calculations |
| spellingShingle | Shigekazu Ito Kohei Yasuda Keisuke Ishihara Victoria L. Karner Kenji M. Kojima Iain McKenzie Muon spectroscopy of a 12-phosphatetraphene with extremely efficient radical trapping properties Scientific Reports Muon Radicals Heterocycles Isotope effects Reaction kinetics DFT calculations |
| title | Muon spectroscopy of a 12-phosphatetraphene with extremely efficient radical trapping properties |
| title_full | Muon spectroscopy of a 12-phosphatetraphene with extremely efficient radical trapping properties |
| title_fullStr | Muon spectroscopy of a 12-phosphatetraphene with extremely efficient radical trapping properties |
| title_full_unstemmed | Muon spectroscopy of a 12-phosphatetraphene with extremely efficient radical trapping properties |
| title_short | Muon spectroscopy of a 12-phosphatetraphene with extremely efficient radical trapping properties |
| title_sort | muon spectroscopy of a 12 phosphatetraphene with extremely efficient radical trapping properties |
| topic | Muon Radicals Heterocycles Isotope effects Reaction kinetics DFT calculations |
| url | https://doi.org/10.1038/s41598-024-84611-w |
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