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Bond-breaking/Bond-forming reactions by vibrational excitation: infrared-induced bidirectional tautomerization of matrix-isolated thiotropolone

2020-10Journal article Restricted
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dc.contributor.authorNunes, Claudio M.
dc.contributor.authorPereira, Nelson A. M.
dc.contributor.authorReva, Igor
dc.contributor.authorAmado, Patrícia
dc.contributor.authorCristiano, Maria De Lurdes
dc.contributor.authorFausto, Rui
dc.date.accessioned2021-06-24T11:35:12Z
dc.date.available2021-06-24T11:35:12Z
dc.date.issued2020-10
dc.description.abstractInfrared vibrational excitation is a promising approach for gaining exceptional control of chemical reactions, in ways that cannot be attained via thermal or electronic excitation. Here, we report an unprecedented example of a bond-breaking/bond-forming reaction by vibrational excitation under matrix isolation conditions. Thiotropolone monomers were isolated in cryogenic argon matrices and characterized by infrared spectroscopy and vibrational computations (harmonic and anharmonic). Narrowband near-infrared irradiations tuned at frequencies of first CH stretching overtone (5940 cm(-1)) or combination modes (5980 cm(-1)) of the OH tautomer, the sole form of the compound that exists in the as-deposited matrices, led to its conversion into the SH tautomer. The tautomerization in the reverse direction was achieved by vibrational excitation of the SH tautomer with irradiation at 5947 or 5994 cm(-1), corresponding to the frequencies of its CH stretching combination and overtone modes. This pioneer demonstration of bidirectional hydroxyl. thiol tautomerization controlled by vibrational excitation creates prospects for new advances in vibrationally induced chemistry.
dc.description.sponsorshipFEDER, via Portugal 2020-POCI [POCI-01-0145-FEDER-028973]
dc.description.sponsorshipPortuguese Foundation for Science and Technology (FCT)Portuguese Foundation for Science and Technology
dc.description.sponsorshipFCTPortuguese Foundation for Science and TechnologyEuropean Commission [UIDB/QUI/0313/2020, UID/MULTI/04326/2019, SFRH/BD/130407/2017]
dc.description.sponsorshipCOMPETE
dc.description.versioninfo:eu-repo/semantics/publishedVersion
dc.identifier.doi10.1021/acs.jpclett.0c02272
dc.identifier.issn1948-7185
dc.identifier.urihttp://hdl.handle.net/10400.1/16371
dc.language.isoeng
dc.peerreviewedyes
dc.publisherAmerican Chemical Society
dc.relationCentre of Marine Sciences
dc.subject.otherChemistry
dc.titleBond-breaking/Bond-forming reactions by vibrational excitation: infrared-induced bidirectional tautomerization of matrix-isolated thiotropolone
dc.typejournal article
dspace.entity.typePublication
oaire.awardTitleCentre of Marine Sciences
oaire.awardURIinfo:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UID%2FMulti%2F04326%2F2019/PT
oaire.citation.endPage8039
oaire.citation.issue19
oaire.citation.startPage8034
oaire.citation.titleJournal of Physical Chemistry Letters
oaire.citation.volume11
oaire.fundingStream6817 - DCRRNI ID
person.familyNameMenalha Amado
person.familyNameCristiano
person.givenNamePatrícia Sofia
person.givenNameMaria de Lurdes
person.identifier.ciencia-id8617-A360-B70A
person.identifier.ciencia-idE411-6006-5A01
person.identifier.orcid0000-0002-7307-9210
person.identifier.orcid0000-0002-9447-2855
person.identifier.ridG-2345-2012
person.identifier.scopus-author-id9238724800
project.funder.identifierhttp://doi.org/10.13039/501100001871
project.funder.nameFundação para a Ciência e a Tecnologia
rcaap.rightsrestrictedAccess
rcaap.typearticle
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relation.isAuthorOfPublicationb16751a6-748e-44b0-9c59-058cbd5b2cc3
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