Conformational Flexibility, UV-Induced Decarbonylation and FT-IR Spectra of 1-Phenyl-1,2 Propanedione in Solid Xenon and in the Low Temperature Amorphous Phase
- Autores
- Lopes, Susy; Gomez Zavaglia, Andrea; Lapinsky, Leszek; Fausto, Rui
- Año de publicación
- 2005
- Idioma
- inglés
- Tipo de recurso
- artículo
- Estado
- versión publicada
- Descripción
- 1-Phenyl-1,2-propanedione has been isolated in low-temperature xenon matrixes and studied by FTIR spectroscopy, supported by DFT(B3LYP)/6-311++G(d,p) calculations. In good agreement with previous electron diffraction data [Shen, Q.; Hagen, K. J. Phys. Chem. 1993, 97, 985], the calculations predicted the existence of only one stable conformation for the compound, in which the O=C-C=O dihedral angle is 135.6 degrees. On the other hand, the experimental data clearly reveals that, in the as-deposited xenon matrixes (T = 20 K), there is a distribution of molecules with different O=C-C=O dihedral angles around the equilibrium value. This distribution results from the efficient trapping of the conformational distribution existing in the gas phase, prior to deposition, which is determined by the low frequency, large amplitude torsional vibration around the C-C central bond. Upon annealing to higher temperatures (T approximately 45 K), the initially trapped conformational distribution can be modified in a certain degree, favoring more polar structures (corresponding to smaller O=C-C=O dihedral angles), as a result of the interactions with the matrix media. Irradiation of the matrix with UV light (lambda > 235 nm) led to decarbonylation of the compound, with generation of acetophenone and carbon monoxide, with an almost complete consumption of the reagent after 1100 min of irradiation (k = 2.8 x 10(-2) min.(-1)). Aggregation of the compound resulting from the matrix warming was also investigated, providing useful information for interpretation of the spectroscopic data obtained for the low-temperature amorphous state of the neat compound.
Fil: Lopes, Susy. 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 Buenos Aires; Argentina
Fil: Lapinsky, Leszek. Polish Academy of Sciences; Argentina
Fil: Fausto, Rui. Universidad de Coimbra; Portugal - Materia
-
FTIR
Matrix isolation - 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:11336/158788
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Conformational Flexibility, UV-Induced Decarbonylation and FT-IR Spectra of 1-Phenyl-1,2 Propanedione in Solid Xenon and in the Low Temperature Amorphous PhaseLopes, SusyGomez Zavaglia, AndreaLapinsky, LeszekFausto, RuiFTIRMatrix isolationhttps://purl.org/becyt/ford/2.11https://purl.org/becyt/ford/21-Phenyl-1,2-propanedione has been isolated in low-temperature xenon matrixes and studied by FTIR spectroscopy, supported by DFT(B3LYP)/6-311++G(d,p) calculations. In good agreement with previous electron diffraction data [Shen, Q.; Hagen, K. J. Phys. Chem. 1993, 97, 985], the calculations predicted the existence of only one stable conformation for the compound, in which the O=C-C=O dihedral angle is 135.6 degrees. On the other hand, the experimental data clearly reveals that, in the as-deposited xenon matrixes (T = 20 K), there is a distribution of molecules with different O=C-C=O dihedral angles around the equilibrium value. This distribution results from the efficient trapping of the conformational distribution existing in the gas phase, prior to deposition, which is determined by the low frequency, large amplitude torsional vibration around the C-C central bond. Upon annealing to higher temperatures (T approximately 45 K), the initially trapped conformational distribution can be modified in a certain degree, favoring more polar structures (corresponding to smaller O=C-C=O dihedral angles), as a result of the interactions with the matrix media. Irradiation of the matrix with UV light (lambda > 235 nm) led to decarbonylation of the compound, with generation of acetophenone and carbon monoxide, with an almost complete consumption of the reagent after 1100 min of irradiation (k = 2.8 x 10(-2) min.(-1)). Aggregation of the compound resulting from the matrix warming was also investigated, providing useful information for interpretation of the spectroscopic data obtained for the low-temperature amorphous state of the neat compound.Fil: Lopes, Susy. 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 Buenos Aires; ArgentinaFil: Lapinsky, Leszek. Polish Academy of Sciences; ArgentinaFil: Fausto, Rui. Universidad de Coimbra; PortugalAmerican Chemical Society2005-06info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/158788Lopes, Susy; Gomez Zavaglia, Andrea; Lapinsky, Leszek; Fausto, Rui; Conformational Flexibility, UV-Induced Decarbonylation and FT-IR Spectra of 1-Phenyl-1,2 Propanedione in Solid Xenon and in the Low Temperature Amorphous Phase; American Chemical Society; Journal of Physical Chemistry A; 109; 25; 6-2005; 5560-55701089-56391520-5215CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jp044287oinfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp044287oinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:38:44Zoai:ri.conicet.gov.ar:11336/158788instacron: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 09:38:44.914CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse |
dc.title.none.fl_str_mv |
Conformational Flexibility, UV-Induced Decarbonylation and FT-IR Spectra of 1-Phenyl-1,2 Propanedione in Solid Xenon and in the Low Temperature Amorphous Phase |
title |
Conformational Flexibility, UV-Induced Decarbonylation and FT-IR Spectra of 1-Phenyl-1,2 Propanedione in Solid Xenon and in the Low Temperature Amorphous Phase |
spellingShingle |
Conformational Flexibility, UV-Induced Decarbonylation and FT-IR Spectra of 1-Phenyl-1,2 Propanedione in Solid Xenon and in the Low Temperature Amorphous Phase Lopes, Susy FTIR Matrix isolation |
title_short |
Conformational Flexibility, UV-Induced Decarbonylation and FT-IR Spectra of 1-Phenyl-1,2 Propanedione in Solid Xenon and in the Low Temperature Amorphous Phase |
title_full |
Conformational Flexibility, UV-Induced Decarbonylation and FT-IR Spectra of 1-Phenyl-1,2 Propanedione in Solid Xenon and in the Low Temperature Amorphous Phase |
title_fullStr |
Conformational Flexibility, UV-Induced Decarbonylation and FT-IR Spectra of 1-Phenyl-1,2 Propanedione in Solid Xenon and in the Low Temperature Amorphous Phase |
title_full_unstemmed |
Conformational Flexibility, UV-Induced Decarbonylation and FT-IR Spectra of 1-Phenyl-1,2 Propanedione in Solid Xenon and in the Low Temperature Amorphous Phase |
title_sort |
Conformational Flexibility, UV-Induced Decarbonylation and FT-IR Spectra of 1-Phenyl-1,2 Propanedione in Solid Xenon and in the Low Temperature Amorphous Phase |
dc.creator.none.fl_str_mv |
Lopes, Susy Gomez Zavaglia, Andrea Lapinsky, Leszek Fausto, Rui |
author |
Lopes, Susy |
author_facet |
Lopes, Susy Gomez Zavaglia, Andrea Lapinsky, Leszek Fausto, Rui |
author_role |
author |
author2 |
Gomez Zavaglia, Andrea Lapinsky, Leszek Fausto, Rui |
author2_role |
author author author |
dc.subject.none.fl_str_mv |
FTIR Matrix isolation |
topic |
FTIR Matrix isolation |
purl_subject.fl_str_mv |
https://purl.org/becyt/ford/2.11 https://purl.org/becyt/ford/2 |
dc.description.none.fl_txt_mv |
1-Phenyl-1,2-propanedione has been isolated in low-temperature xenon matrixes and studied by FTIR spectroscopy, supported by DFT(B3LYP)/6-311++G(d,p) calculations. In good agreement with previous electron diffraction data [Shen, Q.; Hagen, K. J. Phys. Chem. 1993, 97, 985], the calculations predicted the existence of only one stable conformation for the compound, in which the O=C-C=O dihedral angle is 135.6 degrees. On the other hand, the experimental data clearly reveals that, in the as-deposited xenon matrixes (T = 20 K), there is a distribution of molecules with different O=C-C=O dihedral angles around the equilibrium value. This distribution results from the efficient trapping of the conformational distribution existing in the gas phase, prior to deposition, which is determined by the low frequency, large amplitude torsional vibration around the C-C central bond. Upon annealing to higher temperatures (T approximately 45 K), the initially trapped conformational distribution can be modified in a certain degree, favoring more polar structures (corresponding to smaller O=C-C=O dihedral angles), as a result of the interactions with the matrix media. Irradiation of the matrix with UV light (lambda > 235 nm) led to decarbonylation of the compound, with generation of acetophenone and carbon monoxide, with an almost complete consumption of the reagent after 1100 min of irradiation (k = 2.8 x 10(-2) min.(-1)). Aggregation of the compound resulting from the matrix warming was also investigated, providing useful information for interpretation of the spectroscopic data obtained for the low-temperature amorphous state of the neat compound. Fil: Lopes, Susy. 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 Buenos Aires; Argentina Fil: Lapinsky, Leszek. Polish Academy of Sciences; Argentina Fil: Fausto, Rui. Universidad de Coimbra; Portugal |
description |
1-Phenyl-1,2-propanedione has been isolated in low-temperature xenon matrixes and studied by FTIR spectroscopy, supported by DFT(B3LYP)/6-311++G(d,p) calculations. In good agreement with previous electron diffraction data [Shen, Q.; Hagen, K. J. Phys. Chem. 1993, 97, 985], the calculations predicted the existence of only one stable conformation for the compound, in which the O=C-C=O dihedral angle is 135.6 degrees. On the other hand, the experimental data clearly reveals that, in the as-deposited xenon matrixes (T = 20 K), there is a distribution of molecules with different O=C-C=O dihedral angles around the equilibrium value. This distribution results from the efficient trapping of the conformational distribution existing in the gas phase, prior to deposition, which is determined by the low frequency, large amplitude torsional vibration around the C-C central bond. Upon annealing to higher temperatures (T approximately 45 K), the initially trapped conformational distribution can be modified in a certain degree, favoring more polar structures (corresponding to smaller O=C-C=O dihedral angles), as a result of the interactions with the matrix media. Irradiation of the matrix with UV light (lambda > 235 nm) led to decarbonylation of the compound, with generation of acetophenone and carbon monoxide, with an almost complete consumption of the reagent after 1100 min of irradiation (k = 2.8 x 10(-2) min.(-1)). Aggregation of the compound resulting from the matrix warming was also investigated, providing useful information for interpretation of the spectroscopic data obtained for the low-temperature amorphous state of the neat compound. |
publishDate |
2005 |
dc.date.none.fl_str_mv |
2005-06 |
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/11336/158788 Lopes, Susy; Gomez Zavaglia, Andrea; Lapinsky, Leszek; Fausto, Rui; Conformational Flexibility, UV-Induced Decarbonylation and FT-IR Spectra of 1-Phenyl-1,2 Propanedione in Solid Xenon and in the Low Temperature Amorphous Phase; American Chemical Society; Journal of Physical Chemistry A; 109; 25; 6-2005; 5560-5570 1089-5639 1520-5215 CONICET Digital CONICET |
url |
http://hdl.handle.net/11336/158788 |
identifier_str_mv |
Lopes, Susy; Gomez Zavaglia, Andrea; Lapinsky, Leszek; Fausto, Rui; Conformational Flexibility, UV-Induced Decarbonylation and FT-IR Spectra of 1-Phenyl-1,2 Propanedione in Solid Xenon and in the Low Temperature Amorphous Phase; American Chemical Society; Journal of Physical Chemistry A; 109; 25; 6-2005; 5560-5570 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/jp044287o info:eu-repo/semantics/altIdentifier/doi/10.1021/jp044287o |
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 |
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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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1844613224614330368 |
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13.070432 |