Photo release of nitrous oxide from the hyponitrite ion studied by infrared spectroscopy: evidence for the generation of a cobalt-N2O complex: experimental and DFT calculations

Autores
Chacón Villalba, María Elizabeth; Franca, Carlos Alberto; Güida, Jorge Alberto
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The solid state photolysis of sodium, silver and thallium hyponitrite (M2N2O2, M = Na, Ag, Tl) salts and a binuclear complex of cobalt bridged by hyponitrite ([Co(NH3)5-N(O)-NO-Co(NH3)5]4+) were studied by irradiationwith visible and UV light in the electronic absorption region. The UV–visible spectra for free hyponitrite ion and binuclear complex of cobalt were interpreted in terms of Density Functional Theory calculations in order to explain photolysis behavior. The photolysis of each compound depends selectively on the irradiation wavelength. Irradiation with 340–460 nm light and with the 488 nm laser line generates photolysis only in silver and thallium hyponitrite salts, while 253.7 nm light photolyzed all the studied compounds. Infrared spectroscopy was used to followthe photolysis process and to identify the generated products. Remarkably, gaseous N2Owas detected after photolysis in the infrared spectra of sodium, silver, and thalliumhyponitrite KBr pellets. The spectra for [Co(NH3)5-N(O)-NO-Co(NH3)5]4+ suggest that one cobalt ion remains bonded toN2O from which the generation of a [(NH3)5CoNNO]+3 complex is inferred. Density Functional Theory (DFT) based calculations confirm the stability of this last complex and provide the theoretical data which are used in the interpretation of the electronic spectra of the hyponitrite ion and the cobalt binuclear complex and thus in the elucidation of their photolysis behavior. Carbonate ion is also detected after photolysis in all studied compounds, presumably due to the reaction of atmospheric CO2 with the microcrystal surface reaction products. Kinetic measurements for the photolysis of the binuclear complex suggest a first order law for the intensity decay of the hyponitrite IR bands and for the intensity increase in the N2O generation. Predicted and experimental data are in very good agreement.
Centro de Química Inorgánica
Materia
Química
Física
Nitrous oxide complexes
Hyponitrite
Cobalt binuclear complex
Solid state photolysisInfrared spectroscopy
Quantum chemical calculations
DFT
Nivel de accesibilidad
acceso abierto
Condiciones de uso
http://creativecommons.org/licenses/by-nc-sa/4.0/
Repositorio
SEDICI (UNLP)
Institución
Universidad Nacional de La Plata
OAI Identificador
oai:sedici.unlp.edu.ar:10915/104767

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oai_identifier_str oai:sedici.unlp.edu.ar:10915/104767
network_acronym_str SEDICI
repository_id_str 1329
network_name_str SEDICI (UNLP)
spelling Photo release of nitrous oxide from the hyponitrite ion studied by infrared spectroscopy: evidence for the generation of a cobalt-N2O complex: experimental and DFT calculationsChacón Villalba, María ElizabethFranca, Carlos AlbertoGüida, Jorge AlbertoQuímicaFísicaNitrous oxide complexesHyponitriteCobalt binuclear complexSolid state photolysisInfrared spectroscopyQuantum chemical calculationsDFTThe solid state photolysis of sodium, silver and thallium hyponitrite (M2N2O2, M = Na, Ag, Tl) salts and a binuclear complex of cobalt bridged by hyponitrite ([Co(NH3)5-N(O)-NO-Co(NH3)5]4+) were studied by irradiationwith visible and UV light in the electronic absorption region. The UV–visible spectra for free hyponitrite ion and binuclear complex of cobalt were interpreted in terms of Density Functional Theory calculations in order to explain photolysis behavior. The photolysis of each compound depends selectively on the irradiation wavelength. Irradiation with 340–460 nm light and with the 488 nm laser line generates photolysis only in silver and thallium hyponitrite salts, while 253.7 nm light photolyzed all the studied compounds. Infrared spectroscopy was used to followthe photolysis process and to identify the generated products. Remarkably, gaseous N2Owas detected after photolysis in the infrared spectra of sodium, silver, and thalliumhyponitrite KBr pellets. The spectra for [Co(NH3)5-N(O)-NO-Co(NH3)5]4+ suggest that one cobalt ion remains bonded toN2O from which the generation of a [(NH3)5CoNNO]+3 complex is inferred. Density Functional Theory (DFT) based calculations confirm the stability of this last complex and provide the theoretical data which are used in the interpretation of the electronic spectra of the hyponitrite ion and the cobalt binuclear complex and thus in the elucidation of their photolysis behavior. Carbonate ion is also detected after photolysis in all studied compounds, presumably due to the reaction of atmospheric CO2 with the microcrystal surface reaction products. Kinetic measurements for the photolysis of the binuclear complex suggest a first order law for the intensity decay of the hyponitrite IR bands and for the intensity increase in the N2O generation. Predicted and experimental data are in very good agreement.Centro de Química Inorgánica2017-04info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdf189-196http://sedici.unlp.edu.ar/handle/10915/104767enginfo:eu-repo/semantics/altIdentifier/issn/1386-1425info:eu-repo/semantics/altIdentifier/doi/10.1016/j.saa.2017.01.003info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-sa/4.0/Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)reponame:SEDICI (UNLP)instname:Universidad Nacional de La Platainstacron:UNLP2025-09-29T11:22:57Zoai:sedici.unlp.edu.ar:10915/104767Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292025-09-29 11:22:57.932SEDICI (UNLP) - Universidad Nacional de La Platafalse
dc.title.none.fl_str_mv Photo release of nitrous oxide from the hyponitrite ion studied by infrared spectroscopy: evidence for the generation of a cobalt-N2O complex: experimental and DFT calculations
title Photo release of nitrous oxide from the hyponitrite ion studied by infrared spectroscopy: evidence for the generation of a cobalt-N2O complex: experimental and DFT calculations
spellingShingle Photo release of nitrous oxide from the hyponitrite ion studied by infrared spectroscopy: evidence for the generation of a cobalt-N2O complex: experimental and DFT calculations
Chacón Villalba, María Elizabeth
Química
Física
Nitrous oxide complexes
Hyponitrite
Cobalt binuclear complex
Solid state photolysisInfrared spectroscopy
Quantum chemical calculations
DFT
title_short Photo release of nitrous oxide from the hyponitrite ion studied by infrared spectroscopy: evidence for the generation of a cobalt-N2O complex: experimental and DFT calculations
title_full Photo release of nitrous oxide from the hyponitrite ion studied by infrared spectroscopy: evidence for the generation of a cobalt-N2O complex: experimental and DFT calculations
title_fullStr Photo release of nitrous oxide from the hyponitrite ion studied by infrared spectroscopy: evidence for the generation of a cobalt-N2O complex: experimental and DFT calculations
title_full_unstemmed Photo release of nitrous oxide from the hyponitrite ion studied by infrared spectroscopy: evidence for the generation of a cobalt-N2O complex: experimental and DFT calculations
title_sort Photo release of nitrous oxide from the hyponitrite ion studied by infrared spectroscopy: evidence for the generation of a cobalt-N2O complex: experimental and DFT calculations
dc.creator.none.fl_str_mv Chacón Villalba, María Elizabeth
Franca, Carlos Alberto
Güida, Jorge Alberto
author Chacón Villalba, María Elizabeth
author_facet Chacón Villalba, María Elizabeth
Franca, Carlos Alberto
Güida, Jorge Alberto
author_role author
author2 Franca, Carlos Alberto
Güida, Jorge Alberto
author2_role author
author
dc.subject.none.fl_str_mv Química
Física
Nitrous oxide complexes
Hyponitrite
Cobalt binuclear complex
Solid state photolysisInfrared spectroscopy
Quantum chemical calculations
DFT
topic Química
Física
Nitrous oxide complexes
Hyponitrite
Cobalt binuclear complex
Solid state photolysisInfrared spectroscopy
Quantum chemical calculations
DFT
dc.description.none.fl_txt_mv The solid state photolysis of sodium, silver and thallium hyponitrite (M2N2O2, M = Na, Ag, Tl) salts and a binuclear complex of cobalt bridged by hyponitrite ([Co(NH3)5-N(O)-NO-Co(NH3)5]4+) were studied by irradiationwith visible and UV light in the electronic absorption region. The UV–visible spectra for free hyponitrite ion and binuclear complex of cobalt were interpreted in terms of Density Functional Theory calculations in order to explain photolysis behavior. The photolysis of each compound depends selectively on the irradiation wavelength. Irradiation with 340–460 nm light and with the 488 nm laser line generates photolysis only in silver and thallium hyponitrite salts, while 253.7 nm light photolyzed all the studied compounds. Infrared spectroscopy was used to followthe photolysis process and to identify the generated products. Remarkably, gaseous N2Owas detected after photolysis in the infrared spectra of sodium, silver, and thalliumhyponitrite KBr pellets. The spectra for [Co(NH3)5-N(O)-NO-Co(NH3)5]4+ suggest that one cobalt ion remains bonded toN2O from which the generation of a [(NH3)5CoNNO]+3 complex is inferred. Density Functional Theory (DFT) based calculations confirm the stability of this last complex and provide the theoretical data which are used in the interpretation of the electronic spectra of the hyponitrite ion and the cobalt binuclear complex and thus in the elucidation of their photolysis behavior. Carbonate ion is also detected after photolysis in all studied compounds, presumably due to the reaction of atmospheric CO2 with the microcrystal surface reaction products. Kinetic measurements for the photolysis of the binuclear complex suggest a first order law for the intensity decay of the hyponitrite IR bands and for the intensity increase in the N2O generation. Predicted and experimental data are in very good agreement.
Centro de Química Inorgánica
description The solid state photolysis of sodium, silver and thallium hyponitrite (M2N2O2, M = Na, Ag, Tl) salts and a binuclear complex of cobalt bridged by hyponitrite ([Co(NH3)5-N(O)-NO-Co(NH3)5]4+) were studied by irradiationwith visible and UV light in the electronic absorption region. The UV–visible spectra for free hyponitrite ion and binuclear complex of cobalt were interpreted in terms of Density Functional Theory calculations in order to explain photolysis behavior. The photolysis of each compound depends selectively on the irradiation wavelength. Irradiation with 340–460 nm light and with the 488 nm laser line generates photolysis only in silver and thallium hyponitrite salts, while 253.7 nm light photolyzed all the studied compounds. Infrared spectroscopy was used to followthe photolysis process and to identify the generated products. Remarkably, gaseous N2Owas detected after photolysis in the infrared spectra of sodium, silver, and thalliumhyponitrite KBr pellets. The spectra for [Co(NH3)5-N(O)-NO-Co(NH3)5]4+ suggest that one cobalt ion remains bonded toN2O from which the generation of a [(NH3)5CoNNO]+3 complex is inferred. Density Functional Theory (DFT) based calculations confirm the stability of this last complex and provide the theoretical data which are used in the interpretation of the electronic spectra of the hyponitrite ion and the cobalt binuclear complex and thus in the elucidation of their photolysis behavior. Carbonate ion is also detected after photolysis in all studied compounds, presumably due to the reaction of atmospheric CO2 with the microcrystal surface reaction products. Kinetic measurements for the photolysis of the binuclear complex suggest a first order law for the intensity decay of the hyponitrite IR bands and for the intensity increase in the N2O generation. Predicted and experimental data are in very good agreement.
publishDate 2017
dc.date.none.fl_str_mv 2017-04
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
Articulo
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info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://sedici.unlp.edu.ar/handle/10915/104767
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dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/issn/1386-1425
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.saa.2017.01.003
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-sa/4.0/
Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-sa/4.0/
Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
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189-196
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