Please use this identifier to cite or link to this item: https://hdl.handle.net/10316/101240
Title: Bond-Breaking/Bond-Forming Reactions by Vibrational Excitation: Infrared-Induced Bidirectional Tautomerization of Matrix-Isolated Thiotropolone
Authors: Nunes, Cláudio M 
Pereira, Nelson A M 
Reva, Igor 
Amado, Patrícia S M
Cristiano, Maria L S
Fausto, Rui 
Issue Date: 1-Oct-2020
Publisher: American Chemical Society
Project: info:eu-repo/grantAgreement/POCI-01-0145-FEDER-028973/PT 
UIDB/QUI/0313/2020 
UIDP/QUI/0313/2020 
info:eu-repo/grantAgreement/FCT/UID/MULTI/04326/2019/PT 
Serial title, monograph or event: Journal of Physical Chemistry Letters
Volume: 11
Issue: 19
Abstract: Infrared 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.
URI: https://hdl.handle.net/10316/101240
ISSN: 1948-7185
1948-7185
DOI: 10.1021/acs.jpclett.0c02272
Rights: embargoedAccess
Appears in Collections:I&D CQC - Artigos em Revistas Internacionais

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