Please use this identifier to cite or link to this item:
https://hdl.handle.net/10316/91158
DC Field | Value | Language |
---|---|---|
dc.contributor.author | Brás, Elisa M | - |
dc.contributor.author | Cabral, Lília I. L. | - |
dc.contributor.author | Amado, Patrícia S. M. | - |
dc.contributor.author | Abe, Manabu | - |
dc.contributor.author | Rui Fausto | - |
dc.contributor.author | Cristiano, Maria L. S. | - |
dc.date.accessioned | 2020-10-10T12:57:03Z | - |
dc.date.available | 2020-10-10T12:57:03Z | - |
dc.date.issued | 2020-05-28 | - |
dc.identifier.issn | 1089-5639 | pt |
dc.identifier.issn | 1520-5215 | pt |
dc.identifier.uri | https://hdl.handle.net/10316/91158 | - |
dc.description.abstract | 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. | pt |
dc.language.iso | eng | pt |
dc.publisher | ACS Publications | pt |
dc.relation | info:eu-repo/grantAgreement/FCT/UID/QUI/0313/2019/PT | pt |
dc.relation | info:eu-repo/grantAgreement/FCT/UID/MULTI/04326/2019/PT | pt |
dc.relation | info:eu-repo/grantAgreement/PTDC/MAR-BIO/4132/2014/PT | pt |
dc.relation | info:eu-repo/grantAgreement/FCT/SFRH/BD/136246/2018 | pt |
dc.relation | info:eu-repo/grantAgreement/FCT/CCMAR/BI/0017/2016 | pt |
dc.relation | info:eu-repo/grantAgreement/PTDC/MAR-BIO/4132/2014 | pt |
dc.relation | info:eu-repo/grantAgreement/FCT/SFRH/BD/130407/2017 | pt |
dc.rights | embargoedAccess | pt |
dc.rights.uri | http://creativecommons.org/licenses/by/4.0/ | pt |
dc.subject | Photodissociation | pt |
dc.subject | Infrared light | pt |
dc.subject | Electron paramagnetic resonance spectroscopy | pt |
dc.subject | Quantum mechanics | pt |
dc.subject | Irradiation | pt |
dc.title | Photoinduced Reactivity in a Dispiro-1,2,4-trioxolane: Adamantane Ring Expansion and First Direct Observation of the Long-Lived Triplet Diradical Intermediates | pt |
dc.type | article | - |
degois.publication.issue | 124 | pt |
degois.publication.title | The Journal of Physical Chemistry. A | pt |
dc.relation.publisherversion | https://pubs.acs.org/doi/abs/10.1021/acs.jpca.0c01974 | pt |
dc.peerreviewed | yes | pt |
dc.identifier.doi | 10.1021/acs.jpca.0c01974 | pt |
degois.publication.volume | 21 | pt |
dc.date.embargo | 2021-05-28 | * |
uc.date.periodoEmbargo | 365 | pt |
item.openairecristype | http://purl.org/coar/resource_type/c_18cf | - |
item.openairetype | article | - |
item.cerifentitytype | Publications | - |
item.grantfulltext | open | - |
item.fulltext | Com Texto completo | - |
item.languageiso639-1 | en | - |
crisitem.author.researchunit | CQC - Coimbra Chemistry Centre | - |
crisitem.author.parentresearchunit | Faculty of Sciences and Technology | - |
crisitem.author.orcid | 0000-0002-8264-6854 | - |
Appears in Collections: | I&D CQC - Artigos em Revistas Internacionais |
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J_Phys_Chem_A_124_2020_4202.pdf | 814.84 kB | Adobe PDF | View/Open |
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