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Título: | Photoinduced Reactivity in a Dispiro-1,2,4-trioxolane: Adamantane Ring Expansion and First Direct Observation of the Long-Lived Triplet Diradical Intermediates | Autor: | Brás, Elisa M Cabral, Lília I. L. Amado, Patrícia S. M. Abe, Manabu Rui Fausto Cristiano, Maria L. S. |
Palavras-chave: | Photodissociation; Infrared light; Electron paramagnetic resonance spectroscopy; Quantum mechanics; Irradiation | Data: | 28-Mai-2020 | Editora: | ACS Publications | Projeto: | info:eu-repo/grantAgreement/FCT/UID/QUI/0313/2019/PT info:eu-repo/grantAgreement/FCT/UID/MULTI/04326/2019/PT info:eu-repo/grantAgreement/PTDC/MAR-BIO/4132/2014/PT info:eu-repo/grantAgreement/FCT/SFRH/BD/136246/2018 info:eu-repo/grantAgreement/FCT/CCMAR/BI/0017/2016 info:eu-repo/grantAgreement/PTDC/MAR-BIO/4132/2014 info:eu-repo/grantAgreement/FCT/SFRH/BD/130407/2017 |
Título da revista, periódico, livro ou evento: | The Journal of Physical Chemistry. A | Volume: | 21 | Número: | 124 | Resumo: | Dispiro-1,2,4-trioxolane, 1, an ozonide with efficient and broad antiparasitic activity, was synthesized and investigated using matrix isolation FTIR and EPR spectroscopies together with both B3LYP/6-311++G(3df,3dp) and M06-2X/6-311++G(3df,3dp) theoretical methods. Irradiations (λ ≥ 290 nm) of the matrix isolated 1 (Ar or N2) afforded exclusively 4-oxahomoadamantan-5-one, 4, and 1,4-cyclohexanedione, 5. These results suggested that the reaction proceeded via a dioxygen-centered diradical intermediate, formed upon homolytic cleavage of the labile peroxide bond, which regioselectively isomerized to form the more stable (secondary carbon-centered)/oxygen-centered diradical. In situ EPR measurements during the photolysis of 1 deposited in a MeTHF-matrix led to the detection of signals corresponding to two triplet species, one of which was short-lived while the other proved to be persistent at 10 K. These observations strongly support the proposed mechanism for the photogeneration of 4 and 5, which involves intramolecular rearrangement of the intermediate diradical species 2 to afford the triplet diradical 3. | URI: | https://hdl.handle.net/10316/91158 | ISSN: | 1089-5639 1520-5215 |
DOI: | 10.1021/acs.jpca.0c01974 | Direitos: | embargoedAccess |
Aparece nas coleções: | I&D CQC - Artigos em Revistas Internacionais |
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J_Phys_Chem_A_124_2020_4202.pdf | 814.84 kB | Adobe PDF | Ver/Abrir |
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