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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/112454
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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 Técnicas2025-09-03T10:07:13Zoai: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:34982025-09-03 10:07:14.182CONICET 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 |
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CONICET Digital (CONICET) |
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CONICET Digital (CONICET) |
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Consejo Nacional de Investigaciones Científicas y Técnicas |
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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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13.13397 |