Inducing molecular reactions by selective vibrational excitation of a remote antenna with near-infrared light

We demonstrate here that selective vibrational excitation of a moiety, remotely attached in relation to the molecular reaction site, might offer a generalized strategy for inducing bond-breaking/bond-forming reactions with exquisite precision. As a proof-of-principle, the electrocyclic ring-expansio...

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Published inChemical communications (Cambridge, England) Vol. 57; no. 75; pp. 957 - 9573
Main Authors Nunes, Cláudio, Pereira, Nelson A. M, Viegas, Luís P, Pinho e Melo, Teresa M. V. D, Fausto, Rui
Format Journal Article
LanguageEnglish
Published CAMBRIDGE Royal Soc Chemistry 21.09.2021
Royal Society of Chemistry
Subjects
Antennas
Chemistry
Chemistry, Multidisciplinary
Excitation
Molecular structure
Near infrared radiation
Physical Sciences
Science & Technology
BIMOLECULAR REACTIONS
ISOMERIZATION
PYRUVIC-ACID
PHOTOCHEMISTRY
HONO
FEMTOSECOND
BOND
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Summary:We demonstrate here that selective vibrational excitation of a moiety, remotely attached in relation to the molecular reaction site, might offer a generalized strategy for inducing bond-breaking/bond-forming reactions with exquisite precision. As a proof-of-principle, the electrocyclic ring-expansion of a benzazirine to a ketenimine was induced, in a cryogenic matrix, by near-IR light tuned at the overtone stretching frequency of its OH remote antenna. This accomplishment paves the way for harnessing IR vibrational excitation as a tool to guide a variety of molecular structure manipulations in an exceptional highly-selective manner. Ring-expansion of a benzazirine by IR-light tuned at the overtone stretching frequency of its OH remote antenna. Proof-of-principle demonstration for harnessing the power of IR vibrational excitation to guide reactions in unprecedented selective way.
Bibliography:10.1039/d1cc03574f
Electronic supplementary information (ESI) available: For experimental and computational methods, additional figures, tables, and computational data. See DOI
ObjectType-Article-1
SourceType-Scholarly Journals-1
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ISSN:1359-7345
1364-548X
DOI:10.1039/d1cc03574f