Electron spin polarization in the triplet state of methoxy-substituted phosphorus(V) tetraphenyl porphyrins
Photoexcited triplet states of porphyrins are of great relevance in various applications due to their high yield, long lifetime, and strong electron spin polarization. This study delves into properties and spin dynamics of the triplet state of a series of hypervalent phosphorus(V) porphyrins. Transi...
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| Format: | Article |
| Language: | English |
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Elsevier
2024-12-01
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| Series: | Journal of Magnetic Resonance Open |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S2666441024000244 |
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| author | D. Panariti B.J. Bayard A. Barbon Y.E. Kandrashkin P.K. Poddutoori A. van der Est M. Di Valentin |
| author_facet | D. Panariti B.J. Bayard A. Barbon Y.E. Kandrashkin P.K. Poddutoori A. van der Est M. Di Valentin |
| author_sort | D. Panariti |
| collection | DOAJ |
| description | Photoexcited triplet states of porphyrins are of great relevance in various applications due to their high yield, long lifetime, and strong electron spin polarization. This study delves into properties and spin dynamics of the triplet state of a series of hypervalent phosphorus(V) porphyrins. Transient Electron Paramagnetic Resonance (TrEPR) measurements, supported by quantum chemical calculations as well as by optical absorption/luminescence experiments, reveal that, unlike singlet states, the lowest triplet state does not exhibit charge-transfer (CT) character upon photoexcitation. However, the presence of excited CT singlet states alters the intersystem crossing in phosphorus(V) porphyrins, leading to a sign change in the initial multiplet polarization of the photoexcited triplet state. TrEPR results further demonstrate that significant net polarization develops in the triplet states of the phosphorus(V) porphyrins due to the dynamic Jahn-Teller effect. Yet, this effect remains largely unaffected by differences in their molecular structures. |
| format | Article |
| id | doaj-art-1cc1ff82539a49ecbfbfee4b5f9fcd57 |
| institution | Kabale University |
| issn | 2666-4410 |
| language | English |
| publishDate | 2024-12-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Journal of Magnetic Resonance Open |
| spelling | doaj-art-1cc1ff82539a49ecbfbfee4b5f9fcd572024-12-13T11:04:58ZengElsevierJournal of Magnetic Resonance Open2666-44102024-12-0121100169Electron spin polarization in the triplet state of methoxy-substituted phosphorus(V) tetraphenyl porphyrinsD. Panariti0B.J. Bayard1A. Barbon2Y.E. Kandrashkin3P.K. Poddutoori4A. van der Est5M. Di Valentin6Department of Chemical Sciences, University of Padova, Marzolo 1, 35131, Padua, ItalyDepartment of Chemistry & Biochemistry, University of Minnesota Duluth, Duluth, MN, 55812, United StatesDepartment of Chemical Sciences, University of Padova, Marzolo 1, 35131, Padua, ItalyZavoisky Physical-Technical Institute, FRC Kazan Scientific Center of RAS, Sibirsky Tract 10/7, Kazan, 420029, Russian FederationDepartment of Chemistry & Biochemistry, University of Minnesota Duluth, Duluth, MN, 55812, United StatesDepartment of Chemistry, Brock University, 1812 Sir Isaac Brock Way, St. Catharines, Ontario, L2S 3A1, Canada; Corresponding authors.Department of Chemical Sciences, University of Padova, Marzolo 1, 35131, Padua, Italy; Corresponding authors.Photoexcited triplet states of porphyrins are of great relevance in various applications due to their high yield, long lifetime, and strong electron spin polarization. This study delves into properties and spin dynamics of the triplet state of a series of hypervalent phosphorus(V) porphyrins. Transient Electron Paramagnetic Resonance (TrEPR) measurements, supported by quantum chemical calculations as well as by optical absorption/luminescence experiments, reveal that, unlike singlet states, the lowest triplet state does not exhibit charge-transfer (CT) character upon photoexcitation. However, the presence of excited CT singlet states alters the intersystem crossing in phosphorus(V) porphyrins, leading to a sign change in the initial multiplet polarization of the photoexcited triplet state. TrEPR results further demonstrate that significant net polarization develops in the triplet states of the phosphorus(V) porphyrins due to the dynamic Jahn-Teller effect. Yet, this effect remains largely unaffected by differences in their molecular structures.http://www.sciencedirect.com/science/article/pii/S2666441024000244EPRTriplet statePhosphorus porphyrinsElectron spin polarizationRadical hyperpolarizationIntersystem crossing |
| spellingShingle | D. Panariti B.J. Bayard A. Barbon Y.E. Kandrashkin P.K. Poddutoori A. van der Est M. Di Valentin Electron spin polarization in the triplet state of methoxy-substituted phosphorus(V) tetraphenyl porphyrins Journal of Magnetic Resonance Open EPR Triplet state Phosphorus porphyrins Electron spin polarization Radical hyperpolarization Intersystem crossing |
| title | Electron spin polarization in the triplet state of methoxy-substituted phosphorus(V) tetraphenyl porphyrins |
| title_full | Electron spin polarization in the triplet state of methoxy-substituted phosphorus(V) tetraphenyl porphyrins |
| title_fullStr | Electron spin polarization in the triplet state of methoxy-substituted phosphorus(V) tetraphenyl porphyrins |
| title_full_unstemmed | Electron spin polarization in the triplet state of methoxy-substituted phosphorus(V) tetraphenyl porphyrins |
| title_short | Electron spin polarization in the triplet state of methoxy-substituted phosphorus(V) tetraphenyl porphyrins |
| title_sort | electron spin polarization in the triplet state of methoxy substituted phosphorus v tetraphenyl porphyrins |
| topic | EPR Triplet state Phosphorus porphyrins Electron spin polarization Radical hyperpolarization Intersystem crossing |
| url | http://www.sciencedirect.com/science/article/pii/S2666441024000244 |
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