Switching on H-Tunneling through Conformational Control

Detalhes bibliográficos
Autor(a) principal: Roque, José P. L.
Data de Publicação: 2021
Outros Autores: Nunes, Cláudio M., Viegas, Luís P., Pereira, Nelson A. M., Pinho e Melo, Teresa M. V. D., Schreiner, Peter R., Fausto, Rui
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
Texto Completo: http://hdl.handle.net/10316/101242
https://doi.org/10.1021/jacs.1c04329
Resumo: H-tunneling is a ubiquitous phenomenon, relevant to fields from biochemistry to materials science, but harnessing it for mastering the manipulation of chemical structures still remains nearly illusory. Here, we demonstrate how to switch on H-tunneling by conformational control using external radiation. This is outlined with a triplet 2-hydroxyphenylnitrene generated in an N2 matrix at 10 K by UV-irradiation of an azide precursor. The anti-orientation of the nitrene's OH moiety was converted to syn by selective vibrational excitation at the 2ν(OH) frequency, thereby moving the H atom closer to the vicinal nitrene center. This triggers spontaneous H-tunneling to a singlet 6-imino-2,4-cyclohexadienone. Computations reveal that such fast H-tunneling occurs through crossing the triplet-to-singlet potential energy surfaces. Our experimental realization provides an exciting novel strategy to attain control over tunneling, opening new avenues for directing chemical transformations.
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spelling Switching on H-Tunneling through Conformational ControlH-tunneling is a ubiquitous phenomenon, relevant to fields from biochemistry to materials science, but harnessing it for mastering the manipulation of chemical structures still remains nearly illusory. Here, we demonstrate how to switch on H-tunneling by conformational control using external radiation. This is outlined with a triplet 2-hydroxyphenylnitrene generated in an N2 matrix at 10 K by UV-irradiation of an azide precursor. The anti-orientation of the nitrene's OH moiety was converted to syn by selective vibrational excitation at the 2ν(OH) frequency, thereby moving the H atom closer to the vicinal nitrene center. This triggers spontaneous H-tunneling to a singlet 6-imino-2,4-cyclohexadienone. Computations reveal that such fast H-tunneling occurs through crossing the triplet-to-singlet potential energy surfaces. Our experimental realization provides an exciting novel strategy to attain control over tunneling, opening new avenues for directing chemical transformations.American Chemical Society2021info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://hdl.handle.net/10316/101242http://hdl.handle.net/10316/101242https://doi.org/10.1021/jacs.1c04329eng0002-78631520-5126https://doi.org/10.1021/jacs.1c04329Roque, José P. L.Nunes, Cláudio M.Viegas, Luís P.Pereira, Nelson A. M.Pinho e Melo, Teresa M. V. D.Schreiner, Peter R.Fausto, Ruiinfo:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2023-07-17T08:50:37Zoai:estudogeral.uc.pt:10316/101242Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T21:18:28.362714Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse
dc.title.none.fl_str_mv Switching on H-Tunneling through Conformational Control
title Switching on H-Tunneling through Conformational Control
spellingShingle Switching on H-Tunneling through Conformational Control
Roque, José P. L.
title_short Switching on H-Tunneling through Conformational Control
title_full Switching on H-Tunneling through Conformational Control
title_fullStr Switching on H-Tunneling through Conformational Control
title_full_unstemmed Switching on H-Tunneling through Conformational Control
title_sort Switching on H-Tunneling through Conformational Control
author Roque, José P. L.
author_facet Roque, José P. L.
Nunes, Cláudio M.
Viegas, Luís P.
Pereira, Nelson A. M.
Pinho e Melo, Teresa M. V. D.
Schreiner, Peter R.
Fausto, Rui
author_role author
author2 Nunes, Cláudio M.
Viegas, Luís P.
Pereira, Nelson A. M.
Pinho e Melo, Teresa M. V. D.
Schreiner, Peter R.
Fausto, Rui
author2_role author
author
author
author
author
author
dc.contributor.author.fl_str_mv Roque, José P. L.
Nunes, Cláudio M.
Viegas, Luís P.
Pereira, Nelson A. M.
Pinho e Melo, Teresa M. V. D.
Schreiner, Peter R.
Fausto, Rui
description H-tunneling is a ubiquitous phenomenon, relevant to fields from biochemistry to materials science, but harnessing it for mastering the manipulation of chemical structures still remains nearly illusory. Here, we demonstrate how to switch on H-tunneling by conformational control using external radiation. This is outlined with a triplet 2-hydroxyphenylnitrene generated in an N2 matrix at 10 K by UV-irradiation of an azide precursor. The anti-orientation of the nitrene's OH moiety was converted to syn by selective vibrational excitation at the 2ν(OH) frequency, thereby moving the H atom closer to the vicinal nitrene center. This triggers spontaneous H-tunneling to a singlet 6-imino-2,4-cyclohexadienone. Computations reveal that such fast H-tunneling occurs through crossing the triplet-to-singlet potential energy surfaces. Our experimental realization provides an exciting novel strategy to attain control over tunneling, opening new avenues for directing chemical transformations.
publishDate 2021
dc.date.none.fl_str_mv 2021
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dc.type.driver.fl_str_mv info:eu-repo/semantics/article
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status_str publishedVersion
dc.identifier.uri.fl_str_mv http://hdl.handle.net/10316/101242
http://hdl.handle.net/10316/101242
https://doi.org/10.1021/jacs.1c04329
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https://doi.org/10.1021/jacs.1c04329
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1520-5126
https://doi.org/10.1021/jacs.1c04329
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dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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