Photochemistry and Vibrational Spectra of 5-Ethoxy-1-Phenyl-1H-Tetrazole

Autores
Frija, Luís M.T.; Reva, I.D.; Gomez Zavaglia, Andrea; Cristiano, M.L.S.; Fausto, Rui
Año de publicación
2007
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
A combined matrix isolation FT-IR and theoretical DFT(B3LYP)/6-311++G(d,p) study of the molecular structure and photochemistry of 5-ethoxy-1-phenyl-1H-tetrazole (5EPT) was performed. A new method of synthesis of the compound is described. Calculations show three minima, very close in energy and separated by low-energy barriers (less than 4 kJ mol-1), in the ground-state potential energy profile of the molecule. The method of matrix isolation enabled the reduction of the number of populated conformational states in the experiment at low temperature due to the effect known as conformational cooling. As a result, the spectrum of the as-deposited matrix of 5EPT closely matches that of the most stable conformer predicted theoretically, pointing to the existence of only this conformer in the low-temperature matrixes. In this structure, the dihedral angle between the two rings, phenyl and tetrazole, is ca. 30 degrees, whereas the ethyl group stays nearly in the plane of the tetrazole ring and is as far as possible from the phenyl group. In situ UV irradiation (lambda > 235 nm) of the matrix-isolated 5EPT induced unimolecular decomposition, which led mainly to production of ethylcyanate and phenylazide, this later compound further reacting to yield, as final product, 1-aza-1,2,4,6-cycloheptatetraene. Anti-aromatic 3-ethoxy-1-phenyl-1H-diazirene was also observed experimentally as minor photoproduct, resulting from direct extrusion of molecular nitrogen from 5EPT. This species has not been described before and is now characterized by infrared spectroscopy for the first time.
Fil: Frija, Luís M.T.. Universidad de Algarve; Portugal. Universidad de Coimbra; Portugal
Fil: Reva, I.D.. Universidad de Coimbra; Portugal
Fil: Gomez Zavaglia, Andrea. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos; Argentina. Universidad de Coimbra; Portugal. Universidad de Buenos Aires; Argentina
Fil: Cristiano, M.L.S.. Universidad de Algarve; Portugal
Fil: Fausto, Rui. Universidad de Coimbra; Portugal
Materia
Matrix isolation spectroscopy
Photochemistry
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/112454
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Photochemistry and Vibrational Spectra of 5-Ethoxy-1-Phenyl-1H-TetrazoleFrija, Luís M.T.Reva, I.D.Gomez Zavaglia, AndreaCristiano, M.L.S.Fausto, RuiMatrix isolation spectroscopyPhotochemistryhttps://purl.org/becyt/ford/2.11https://purl.org/becyt/ford/2A combined matrix isolation FT-IR and theoretical DFT(B3LYP)/6-311++G(d,p) study of the molecular structure and photochemistry of 5-ethoxy-1-phenyl-1H-tetrazole (5EPT) was performed. A new method of synthesis of the compound is described. Calculations show three minima, very close in energy and separated by low-energy barriers (less than 4 kJ mol-1), in the ground-state potential energy profile of the molecule. The method of matrix isolation enabled the reduction of the number of populated conformational states in the experiment at low temperature due to the effect known as conformational cooling. As a result, the spectrum of the as-deposited matrix of 5EPT closely matches that of the most stable conformer predicted theoretically, pointing to the existence of only this conformer in the low-temperature matrixes. In this structure, the dihedral angle between the two rings, phenyl and tetrazole, is ca. 30 degrees, whereas the ethyl group stays nearly in the plane of the tetrazole ring and is as far as possible from the phenyl group. In situ UV irradiation (lambda > 235 nm) of the matrix-isolated 5EPT induced unimolecular decomposition, which led mainly to production of ethylcyanate and phenylazide, this later compound further reacting to yield, as final product, 1-aza-1,2,4,6-cycloheptatetraene. Anti-aromatic 3-ethoxy-1-phenyl-1H-diazirene was also observed experimentally as minor photoproduct, resulting from direct extrusion of molecular nitrogen from 5EPT. This species has not been described before and is now characterized by infrared spectroscopy for the first time.Fil: Frija, Luís M.T.. Universidad de Algarve; Portugal. Universidad de Coimbra; PortugalFil: Reva, I.D.. Universidad de Coimbra; PortugalFil: Gomez Zavaglia, Andrea. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos; Argentina. Universidad de Coimbra; Portugal. Universidad de Buenos Aires; ArgentinaFil: Cristiano, M.L.S.. Universidad de Algarve; PortugalFil: Fausto, Rui. Universidad de Coimbra; PortugalAmerican Chemical Society2007-04info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/112454Frija, Luís M.T.; Reva, I.D.; Gomez Zavaglia, Andrea; Cristiano, M.L.S.; Fausto, Rui; Photochemistry and Vibrational Spectra of 5-Ethoxy-1-Phenyl-1H-Tetrazole; American Chemical Society; Journal of Physical Chemistry A; 111; 15; 4-2007; 2879-28881089-56391520-5215CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jp068556hinfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp068556hinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:32:46Zoai:ri.conicet.gov.ar:11336/112454instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 10:32:46.434CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Photochemistry and Vibrational Spectra of 5-Ethoxy-1-Phenyl-1H-Tetrazole
title Photochemistry and Vibrational Spectra of 5-Ethoxy-1-Phenyl-1H-Tetrazole
spellingShingle Photochemistry and Vibrational Spectra of 5-Ethoxy-1-Phenyl-1H-Tetrazole
Frija, Luís M.T.
Matrix isolation spectroscopy
Photochemistry
title_short Photochemistry and Vibrational Spectra of 5-Ethoxy-1-Phenyl-1H-Tetrazole
title_full Photochemistry and Vibrational Spectra of 5-Ethoxy-1-Phenyl-1H-Tetrazole
title_fullStr Photochemistry and Vibrational Spectra of 5-Ethoxy-1-Phenyl-1H-Tetrazole
title_full_unstemmed Photochemistry and Vibrational Spectra of 5-Ethoxy-1-Phenyl-1H-Tetrazole
title_sort Photochemistry and Vibrational Spectra of 5-Ethoxy-1-Phenyl-1H-Tetrazole
dc.creator.none.fl_str_mv Frija, Luís M.T.
Reva, I.D.
Gomez Zavaglia, Andrea
Cristiano, M.L.S.
Fausto, Rui
author Frija, Luís M.T.
author_facet Frija, Luís M.T.
Reva, I.D.
Gomez Zavaglia, Andrea
Cristiano, M.L.S.
Fausto, Rui
author_role author
author2 Reva, I.D.
Gomez Zavaglia, Andrea
Cristiano, M.L.S.
Fausto, Rui
author2_role author
author
author
author
dc.subject.none.fl_str_mv Matrix isolation spectroscopy
Photochemistry
topic Matrix isolation spectroscopy
Photochemistry
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.11
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv A combined matrix isolation FT-IR and theoretical DFT(B3LYP)/6-311++G(d,p) study of the molecular structure and photochemistry of 5-ethoxy-1-phenyl-1H-tetrazole (5EPT) was performed. A new method of synthesis of the compound is described. Calculations show three minima, very close in energy and separated by low-energy barriers (less than 4 kJ mol-1), in the ground-state potential energy profile of the molecule. The method of matrix isolation enabled the reduction of the number of populated conformational states in the experiment at low temperature due to the effect known as conformational cooling. As a result, the spectrum of the as-deposited matrix of 5EPT closely matches that of the most stable conformer predicted theoretically, pointing to the existence of only this conformer in the low-temperature matrixes. In this structure, the dihedral angle between the two rings, phenyl and tetrazole, is ca. 30 degrees, whereas the ethyl group stays nearly in the plane of the tetrazole ring and is as far as possible from the phenyl group. In situ UV irradiation (lambda > 235 nm) of the matrix-isolated 5EPT induced unimolecular decomposition, which led mainly to production of ethylcyanate and phenylazide, this later compound further reacting to yield, as final product, 1-aza-1,2,4,6-cycloheptatetraene. Anti-aromatic 3-ethoxy-1-phenyl-1H-diazirene was also observed experimentally as minor photoproduct, resulting from direct extrusion of molecular nitrogen from 5EPT. This species has not been described before and is now characterized by infrared spectroscopy for the first time.
Fil: Frija, Luís M.T.. Universidad de Algarve; Portugal. Universidad de Coimbra; Portugal
Fil: Reva, I.D.. Universidad de Coimbra; Portugal
Fil: Gomez Zavaglia, Andrea. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos; Argentina. Universidad de Coimbra; Portugal. Universidad de Buenos Aires; Argentina
Fil: Cristiano, M.L.S.. Universidad de Algarve; Portugal
Fil: Fausto, Rui. Universidad de Coimbra; Portugal
description A combined matrix isolation FT-IR and theoretical DFT(B3LYP)/6-311++G(d,p) study of the molecular structure and photochemistry of 5-ethoxy-1-phenyl-1H-tetrazole (5EPT) was performed. A new method of synthesis of the compound is described. Calculations show three minima, very close in energy and separated by low-energy barriers (less than 4 kJ mol-1), in the ground-state potential energy profile of the molecule. The method of matrix isolation enabled the reduction of the number of populated conformational states in the experiment at low temperature due to the effect known as conformational cooling. As a result, the spectrum of the as-deposited matrix of 5EPT closely matches that of the most stable conformer predicted theoretically, pointing to the existence of only this conformer in the low-temperature matrixes. In this structure, the dihedral angle between the two rings, phenyl and tetrazole, is ca. 30 degrees, whereas the ethyl group stays nearly in the plane of the tetrazole ring and is as far as possible from the phenyl group. In situ UV irradiation (lambda > 235 nm) of the matrix-isolated 5EPT induced unimolecular decomposition, which led mainly to production of ethylcyanate and phenylazide, this later compound further reacting to yield, as final product, 1-aza-1,2,4,6-cycloheptatetraene. Anti-aromatic 3-ethoxy-1-phenyl-1H-diazirene was also observed experimentally as minor photoproduct, resulting from direct extrusion of molecular nitrogen from 5EPT. This species has not been described before and is now characterized by infrared spectroscopy for the first time.
publishDate 2007
dc.date.none.fl_str_mv 2007-04
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/112454
Frija, Luís M.T.; Reva, I.D.; Gomez Zavaglia, Andrea; Cristiano, M.L.S.; Fausto, Rui; Photochemistry and Vibrational Spectra of 5-Ethoxy-1-Phenyl-1H-Tetrazole; American Chemical Society; Journal of Physical Chemistry A; 111; 15; 4-2007; 2879-2888
1089-5639
1520-5215
CONICET Digital
CONICET
url http://hdl.handle.net/11336/112454
identifier_str_mv Frija, Luís M.T.; Reva, I.D.; Gomez Zavaglia, Andrea; Cristiano, M.L.S.; Fausto, Rui; Photochemistry and Vibrational Spectra of 5-Ethoxy-1-Phenyl-1H-Tetrazole; American Chemical Society; Journal of Physical Chemistry A; 111; 15; 4-2007; 2879-2888
1089-5639
1520-5215
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jp068556h
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp068556h
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.069144

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