Structure, conformational landscape and UV-induced selective rotamerization of 2-aminoacetanilide

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dc.authoridFausto, Rui/0000-0002-8264-6854
dc.authoridBrito, Anna/0000-0003-1686-2740
dc.authoridCatikkas, Berna/0000-0002-0566-5015
dc.authoridLopes, Susy/0000-0002-7631-4597
dc.authoridJustino, Licinia/0000-0002-8338-6441
dc.authoridOgruc Ildiz, Gulce/0000-0002-7827-5050
dc.contributor.authorBrito, Anna Luiza B.
dc.contributor.authorJustino, Licinia L. G.
dc.contributor.authorCatikkas, Berna
dc.contributor.authorLopes, Susy
dc.contributor.authorIldiz, Gulce O.
dc.contributor.authorFausto, Rui
dc.date.accessioned2024-09-18T19:47:57Z
dc.date.available2024-09-18T19:47:57Z
dc.date.issued2023
dc.departmentHatay Mustafa Kemal Üniversitesien_US
dc.description.abstractThe molecular structure, conformational space and UV-induced rotamerization and decarbonylation of 2-aminoacetanilide (2AA) were investigated by matrix isolation infrared spectroscopy and quantum chemical electronic structure calculations. The compound was isolated in a cryogenic (15 K) argon matrix, and four conformers were spectroscopically identified: two trans-amide (O--C-N-H dihedral - 180 degrees) conformers (trans-I and trans-II), and two higher-energy cis-amide (O--C-N-H dihedral - 0 degrees) conformers (cis-I and cis-II). These four conformers were found to be present in the as-deposited matrix of 2AA in a population ratio matching well that predicted by the calculations for the gas-phase equilibrium at the temperature of the vapor of the compound before deposition (60 degrees C = 333.15 K). The calculations predicted also the existence of an additional higherenergy trans-amide conformer (trans-III) which was not observed experimentally. In situ broadband UV irradiation (lambda > 235 nm) of the matrix-isolated compound was found to induce selective conversion of conformer trans-I into conformer trans-II, in a few minutes (55 % after 2 min. of irradiation; 70 % after 10 min.), while the populations of the cis-amide conformers did not change. Prolonged UV irradiation was found to result in decomposition of the compound, leading to generation of carbon monoxide and 2-amine-N-methylaniline. The infrared spectra of the experimentally relevant conformers of 2AA were interpreted and assigned with help of normal coordinate analysis, and the different behavior of the conformers of 2AA upon UV-irradiation of the argon matrix was explained with help of time-dependent DFT (TD-DFT) calculations.en_US
dc.description.sponsorshipFundacao para a Ciencia e a Tecnologia (FCT) [UI0313B/QUI/2020, UI0313P/QUI/ 2020, LA/P/0056/2020]; [PTDC/QUI-QFI/1880/2020]en_US
dc.description.sponsorshipThis work has run within the research project PTDC/QUI-QFI/1880/2020. The CQC-IMS is supported by the Fundacao para a Ciencia e a Tecnologia (FCT), through projects UI0313B/QUI/2020, UI0313P/QUI/ 2020 and LA/P/0056/2020. The authors also acknowledge the Laboratory for Advanced Computing at University of Coimbra (https://www. uc.pt/lca) for providing computing resources.en_US
dc.identifier.doi10.1016/j.jphotochem.2022.114302
dc.identifier.issn1010-6030
dc.identifier.issn1873-2666
dc.identifier.scopus2-s2.0-85139043695en_US
dc.identifier.scopusqualityQ1en_US
dc.identifier.urihttps://doi.org/10.1016/j.jphotochem.2022.114302
dc.identifier.urihttps://hdl.handle.net/20.500.12483/7248
dc.identifier.volume435en_US
dc.identifier.wosWOS:000875761100005en_US
dc.identifier.wosqualityQ2en_US
dc.indekslendigikaynakWeb of Scienceen_US
dc.indekslendigikaynakScopusen_US
dc.language.isoenen_US
dc.publisherElsevier Science Saen_US
dc.relation.ispartofJournal of Photochemistry and Photobiology A-Chemistryen_US
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanıen_US
dc.rightsinfo:eu-repo/semantics/closedAccessen_US
dc.subject2-Aminoacetanilideen_US
dc.subjectMatrix isolationen_US
dc.subjectLow temperature infrared spectraen_US
dc.subjectDFT(B3LYP)en_US
dc.subject6-311++G(dp) calculationsen_US
dc.subjectUV-Induced conformational isomerizationen_US
dc.subjectDecarbonylationen_US
dc.titleStructure, conformational landscape and UV-induced selective rotamerization of 2-aminoacetanilideen_US
dc.typeArticleen_US

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