Structure and UV-induced photochemistry of 2-furaldehyde dimethylhydrazone isolated in rare gas matrices

Autores
Araujo Andrade, C.; Giuliano, B. M.; Gomez Zavaglia, Andrea; Fausto, R.
Año de publicación
2012
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
In this work, a combined matrix isolation FTIR and theoretical DFT(B3LYP)/6-311++G(d,p) study of 2-furaldehyde dimethylhydrazone (2FDH) was performed. According to calculations, two E and two Z conformers exist, the E forms having considerably lower energy than the Z forms. The absence of relevant sterical hindrance between the two substituents around the CN bond (dimethylamino and 2-furyl) in the E structures and an extended π-p electron delocalization in the hydrazone moiety determines the higher stability of these species relatively to the Z structures. In the lowest energy form (E-AG) the O-C-CN and CN-N-Lp (Lp = lone electron pair of amine nitrogen atom) dihedral angles are predicted by the calculations to be -177.2° and 93.7°, respectively. The weak (NC)-H⋯O hydrogen bond type interaction (H⋯O distance: 252.2 pm) in form E-AG, together with the absence in this form of the destabilizing interaction between the lone electron pairs of the oxygen and nitrogen atoms existing in E-SG, explains its lower energy in comparison with this latter form. Both E-AG and E-SG conformers could be trapped from room temperature gas phase in low temperature argon and xenon matrices. The high E-SG → E-AG energy barrier (>25 kJ mol-1) explains that, upon increasing the temperature of the matrices no conformational isomerization could be observed. After irradiation of 2FDH with UV-light at λ > 328 and λ > 234 nm, two different photochemistries were observed. Irradiation at lower energy (λ > 328 nm) induced the E-AG → E-SG isomerization. Further irradiation at higher energy (λ > 234 nm) led to a quick consumption of 2FDH and production of furan and dimethylisocyanide.
Fil: Araujo Andrade, C.. Universidad Autonoma de Zacatecas; México
Fil: Giuliano, B. M.. 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
Fil: Fausto, R.. Universidad de Coimbra; Portugal
Materia
2-Furaldehyde Dimethylhydrazone
Dft(B3lyp)/6-311++G(D,P) Calculations
Infrared Spectroscopy
Matrix Isolation
Photochemistry
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/82362
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/82362
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Structure and UV-induced photochemistry of 2-furaldehyde dimethylhydrazone isolated in rare gas matricesAraujo Andrade, C.Giuliano, B. M.Gomez Zavaglia, AndreaFausto, R.2-Furaldehyde DimethylhydrazoneDft(B3lyp)/6-311++G(D,P) CalculationsInfrared SpectroscopyMatrix IsolationPhotochemistryhttps://purl.org/becyt/ford/2.11https://purl.org/becyt/ford/2In this work, a combined matrix isolation FTIR and theoretical DFT(B3LYP)/6-311++G(d,p) study of 2-furaldehyde dimethylhydrazone (2FDH) was performed. According to calculations, two E and two Z conformers exist, the E forms having considerably lower energy than the Z forms. The absence of relevant sterical hindrance between the two substituents around the CN bond (dimethylamino and 2-furyl) in the E structures and an extended π-p electron delocalization in the hydrazone moiety determines the higher stability of these species relatively to the Z structures. In the lowest energy form (E-AG) the O-C-CN and CN-N-Lp (Lp = lone electron pair of amine nitrogen atom) dihedral angles are predicted by the calculations to be -177.2° and 93.7°, respectively. The weak (NC)-H⋯O hydrogen bond type interaction (H⋯O distance: 252.2 pm) in form E-AG, together with the absence in this form of the destabilizing interaction between the lone electron pairs of the oxygen and nitrogen atoms existing in E-SG, explains its lower energy in comparison with this latter form. Both E-AG and E-SG conformers could be trapped from room temperature gas phase in low temperature argon and xenon matrices. The high E-SG → E-AG energy barrier (>25 kJ mol-1) explains that, upon increasing the temperature of the matrices no conformational isomerization could be observed. After irradiation of 2FDH with UV-light at λ > 328 and λ > 234 nm, two different photochemistries were observed. Irradiation at lower energy (λ > 328 nm) induced the E-AG → E-SG isomerization. Further irradiation at higher energy (λ > 234 nm) led to a quick consumption of 2FDH and production of furan and dimethylisocyanide.Fil: Araujo Andrade, C.. Universidad Autonoma de Zacatecas; MéxicoFil: Giuliano, B. M.. 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; PortugalFil: Fausto, R.. Universidad de Coimbra; PortugalPergamon-Elsevier Science Ltd2012-11info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/82362Araujo Andrade, C.; Giuliano, B. M.; Gomez Zavaglia, Andrea; Fausto, R.; Structure and UV-induced photochemistry of 2-furaldehyde dimethylhydrazone isolated in rare gas matrices; Pergamon-Elsevier Science Ltd; Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy; 97; 11-2012; 830-8371386-1425CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S1386142512006828info:eu-repo/semantics/altIdentifier/doi/10.1016/j.saa.2012.07.061info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-12-23T14:46:45Zoai:ri.conicet.gov.ar:11336/82362instacron: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:34982025-12-23 14:46:45.448CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Structure and UV-induced photochemistry of 2-furaldehyde dimethylhydrazone isolated in rare gas matrices
title Structure and UV-induced photochemistry of 2-furaldehyde dimethylhydrazone isolated in rare gas matrices
spellingShingle Structure and UV-induced photochemistry of 2-furaldehyde dimethylhydrazone isolated in rare gas matrices
Araujo Andrade, C.
2-Furaldehyde Dimethylhydrazone
Dft(B3lyp)/6-311++G(D,P) Calculations
Infrared Spectroscopy
Matrix Isolation
Photochemistry
title_short Structure and UV-induced photochemistry of 2-furaldehyde dimethylhydrazone isolated in rare gas matrices
title_full Structure and UV-induced photochemistry of 2-furaldehyde dimethylhydrazone isolated in rare gas matrices
title_fullStr Structure and UV-induced photochemistry of 2-furaldehyde dimethylhydrazone isolated in rare gas matrices
title_full_unstemmed Structure and UV-induced photochemistry of 2-furaldehyde dimethylhydrazone isolated in rare gas matrices
title_sort Structure and UV-induced photochemistry of 2-furaldehyde dimethylhydrazone isolated in rare gas matrices
dc.creator.none.fl_str_mv Araujo Andrade, C.
Giuliano, B. M.
Gomez Zavaglia, Andrea
Fausto, R.
author Araujo Andrade, C.
author_facet Araujo Andrade, C.
Giuliano, B. M.
Gomez Zavaglia, Andrea
Fausto, R.
author_role author
author2 Giuliano, B. M.
Gomez Zavaglia, Andrea
Fausto, R.
author2_role author
author
author
dc.subject.none.fl_str_mv 2-Furaldehyde Dimethylhydrazone
Dft(B3lyp)/6-311++G(D,P) Calculations
Infrared Spectroscopy
Matrix Isolation
Photochemistry
topic 2-Furaldehyde Dimethylhydrazone
Dft(B3lyp)/6-311++G(D,P) Calculations
Infrared Spectroscopy
Matrix Isolation
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 In this work, a combined matrix isolation FTIR and theoretical DFT(B3LYP)/6-311++G(d,p) study of 2-furaldehyde dimethylhydrazone (2FDH) was performed. According to calculations, two E and two Z conformers exist, the E forms having considerably lower energy than the Z forms. The absence of relevant sterical hindrance between the two substituents around the CN bond (dimethylamino and 2-furyl) in the E structures and an extended π-p electron delocalization in the hydrazone moiety determines the higher stability of these species relatively to the Z structures. In the lowest energy form (E-AG) the O-C-CN and CN-N-Lp (Lp = lone electron pair of amine nitrogen atom) dihedral angles are predicted by the calculations to be -177.2° and 93.7°, respectively. The weak (NC)-H⋯O hydrogen bond type interaction (H⋯O distance: 252.2 pm) in form E-AG, together with the absence in this form of the destabilizing interaction between the lone electron pairs of the oxygen and nitrogen atoms existing in E-SG, explains its lower energy in comparison with this latter form. Both E-AG and E-SG conformers could be trapped from room temperature gas phase in low temperature argon and xenon matrices. The high E-SG → E-AG energy barrier (>25 kJ mol-1) explains that, upon increasing the temperature of the matrices no conformational isomerization could be observed. After irradiation of 2FDH with UV-light at λ > 328 and λ > 234 nm, two different photochemistries were observed. Irradiation at lower energy (λ > 328 nm) induced the E-AG → E-SG isomerization. Further irradiation at higher energy (λ > 234 nm) led to a quick consumption of 2FDH and production of furan and dimethylisocyanide.
Fil: Araujo Andrade, C.. Universidad Autonoma de Zacatecas; México
Fil: Giuliano, B. M.. 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
Fil: Fausto, R.. Universidad de Coimbra; Portugal
description In this work, a combined matrix isolation FTIR and theoretical DFT(B3LYP)/6-311++G(d,p) study of 2-furaldehyde dimethylhydrazone (2FDH) was performed. According to calculations, two E and two Z conformers exist, the E forms having considerably lower energy than the Z forms. The absence of relevant sterical hindrance between the two substituents around the CN bond (dimethylamino and 2-furyl) in the E structures and an extended π-p electron delocalization in the hydrazone moiety determines the higher stability of these species relatively to the Z structures. In the lowest energy form (E-AG) the O-C-CN and CN-N-Lp (Lp = lone electron pair of amine nitrogen atom) dihedral angles are predicted by the calculations to be -177.2° and 93.7°, respectively. The weak (NC)-H⋯O hydrogen bond type interaction (H⋯O distance: 252.2 pm) in form E-AG, together with the absence in this form of the destabilizing interaction between the lone electron pairs of the oxygen and nitrogen atoms existing in E-SG, explains its lower energy in comparison with this latter form. Both E-AG and E-SG conformers could be trapped from room temperature gas phase in low temperature argon and xenon matrices. The high E-SG → E-AG energy barrier (>25 kJ mol-1) explains that, upon increasing the temperature of the matrices no conformational isomerization could be observed. After irradiation of 2FDH with UV-light at λ > 328 and λ > 234 nm, two different photochemistries were observed. Irradiation at lower energy (λ > 328 nm) induced the E-AG → E-SG isomerization. Further irradiation at higher energy (λ > 234 nm) led to a quick consumption of 2FDH and production of furan and dimethylisocyanide.
publishDate 2012
dc.date.none.fl_str_mv 2012-11
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/11336/82362
Araujo Andrade, C.; Giuliano, B. M.; Gomez Zavaglia, Andrea; Fausto, R.; Structure and UV-induced photochemistry of 2-furaldehyde dimethylhydrazone isolated in rare gas matrices; Pergamon-Elsevier Science Ltd; Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy; 97; 11-2012; 830-837
1386-1425
CONICET Digital
CONICET
url http://hdl.handle.net/11336/82362
identifier_str_mv Araujo Andrade, C.; Giuliano, B. M.; Gomez Zavaglia, Andrea; Fausto, R.; Structure and UV-induced photochemistry of 2-furaldehyde dimethylhydrazone isolated in rare gas matrices; Pergamon-Elsevier Science Ltd; Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy; 97; 11-2012; 830-837
1386-1425
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://www.sciencedirect.com/science/article/pii/S1386142512006828
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.saa.2012.07.061
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Pergamon-Elsevier Science Ltd
publisher.none.fl_str_mv Pergamon-Elsevier Science Ltd
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 12.952241

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