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https://hdl.handle.net/10316/101245
Título: | Evidence of IR-Induced Chemistry in a Neat Solid: Tautomerization of Thiotropolone by Thermal, Electronic, and Vibrational Excitations | Autor: | Pereira, Nelson A M Nunes, Cláudio M Reva, Igor Fausto, Rui |
Data: | 29-Jul-2021 | Editora: | American Chemical Society | Projeto: | info:eu-repo/grantAgreement/POCI-01-0145-FEDER-028973/PT PTDC/QUI/QFI/1880/2020 UIDB/00313/2020 UIDB/00102/2020 UIDP/00313/2020 UIDP/00102/2020 |
Título da revista, periódico, livro ou evento: | The Journal of Physical Chemistry A | Volume: | 125 | Número: | 29 | Resumo: | Thiotropolone isolated in argon and xenon matrices (as monomers) or in a neat solid (as the crystalline or amorphous state) at low temperature was found to exist only in the thione-enol form. Visible light irradiation (λ ≥ 400 nm) leads to thione-enol → thiol-keto tautomerization in matrices and under neat solid conditions at 15 K. The assignment of the IR spectra of the two thiotropolone tautomers (thione-enol and thiol-keto) was carried out with the support of B3LYP/6-311+G(2d,p) computations. The thiol-keto form generated in situ in a neat solid was found to tautomerize back to the thione-enol upon annealing up to 100 K. Gaussian-4 (G4) computations estimate that such a tautomerization process has an energy barrier of ∼25 kJ mol-1, which is consistent with the observations. Moreover, it was found that narrowband IR irradiation of the thiol-keto form in a neat solid, at the frequency of its CH stretching overtones/combination modes, also induces tautomerization to the thione-enol form. Such a result constitutes an important demonstration of vibrationally induced chemistry under neat solid conditions. | URI: | https://hdl.handle.net/10316/101245 | ISSN: | 1089-5639 1520-5215 |
DOI: | 10.1021/acs.jpca.1c04081 | Direitos: | embargoedAccess |
Aparece nas coleções: | I&D CQC - Artigos em Revistas Internacionais |
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Ficheiro | Descrição | Tamanho | Formato | |
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JPCA-2021-125-6394.pdf | 2.42 MB | Adobe PDF | Ver/Abrir |
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