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, Elizabeth; Franca, Carlos Alberto; Guida, 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 (M 2 N 2 O 2 , M = Na, Ag, Tl) salts and abinuclear complex of cobalt bridged by hyponitrite ([Co(NH 3 ) 5 -N(O)-NO-Co(NH 3 ) 5 ] 4+ ) were studied by irradi-ation with visible and UV light in the electronic absorption region. The UV?visible spectra for free hyponitrite ionand binuclear complex of cobalt were interpreted in terms of Density Functional Theory calculations in order toexplain photolysis behavior.The photolysis of each compound depends selectively on the irradiation wavelength. Irradiation with340?460 nm light and with the 488 nm laser line generates photolysis only in silver and thalliumhyponitrite salts, while 253.7 nm light photolyzed all the studied compounds.Infrared spectroscopy was used to follow the photolysis process and to identify the generated products. Remark-ably, gaseous N 2 O was detected after photolysis in the infrared spectra of sodium, silver, and thallium hyponitriteKBr pellets. The spectra for [Co(NH 3 ) 5 -N(O)-NO-Co(NH 3 ) 5 ] 4+ suggest that one cobalt ion remains bonded to N 2 Ofrom which the generation of a [(NH 3 ) 5 CoNNO] +3 complex is inferred. Density Functional Theory (DFT) basedcalculations confirm the stability of this last complex and provide the theoretical data which are used in the in-terpretation of the electronic spectra of the hyponitrite ion and the cobalt binuclear complex and thus in the elu-cidation of their photolysis behavior.Carbonate ion is also detected after photolysis in all studied compounds, presumably due to the reaction of atmo-spheric CO 2 with the microcrystal surface reaction products. Kinetic measurements for the photolysis of thebinuclear complex suggest a first order law for the intensity decay of the hyponitrite IR bands and for the inten-sity increase in the N 2 O generation. Predicted and experimental data are in very good agreement.
Fil: Chacón Villalba, Elizabeth. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Franca, Carlos Alberto. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Guida, Jorge Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química; Argentina
Materia
NITROUS OXIDE COMPLEXES
HYPONITRITE
COBALT BINUCLEAR COMPLEX
SOLID STATE PHOTOLYSIS
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
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CONICET Digital (CONICET)
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Consejo Nacional de Investigaciones Científicas y Técnicas
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oai:ri.conicet.gov.ar:11336/255695
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oai_identifier_str oai:ri.conicet.gov.ar:11336/255695
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
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, ElizabethFranca, Carlos AlbertoGuida, Jorge AlbertoNITROUS OXIDE COMPLEXESHYPONITRITECOBALT BINUCLEAR COMPLEXSOLID STATE PHOTOLYSIShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The solid state photolysis of sodium, silver and thallium hyponitrite (M 2 N 2 O 2 , M = Na, Ag, Tl) salts and abinuclear complex of cobalt bridged by hyponitrite ([Co(NH 3 ) 5 -N(O)-NO-Co(NH 3 ) 5 ] 4+ ) were studied by irradi-ation with visible and UV light in the electronic absorption region. The UV?visible spectra for free hyponitrite ionand binuclear complex of cobalt were interpreted in terms of Density Functional Theory calculations in order toexplain photolysis behavior.The photolysis of each compound depends selectively on the irradiation wavelength. Irradiation with340?460 nm light and with the 488 nm laser line generates photolysis only in silver and thalliumhyponitrite salts, while 253.7 nm light photolyzed all the studied compounds.Infrared spectroscopy was used to follow the photolysis process and to identify the generated products. Remark-ably, gaseous N 2 O was detected after photolysis in the infrared spectra of sodium, silver, and thallium hyponitriteKBr pellets. The spectra for [Co(NH 3 ) 5 -N(O)-NO-Co(NH 3 ) 5 ] 4+ suggest that one cobalt ion remains bonded to N 2 Ofrom which the generation of a [(NH 3 ) 5 CoNNO] +3 complex is inferred. Density Functional Theory (DFT) basedcalculations confirm the stability of this last complex and provide the theoretical data which are used in the in-terpretation of the electronic spectra of the hyponitrite ion and the cobalt binuclear complex and thus in the elu-cidation of their photolysis behavior.Carbonate ion is also detected after photolysis in all studied compounds, presumably due to the reaction of atmo-spheric CO 2 with the microcrystal surface reaction products. Kinetic measurements for the photolysis of thebinuclear complex suggest a first order law for the intensity decay of the hyponitrite IR bands and for the inten-sity increase in the N 2 O generation. Predicted and experimental data are in very good agreement.Fil: Chacón Villalba, Elizabeth. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; ArgentinaFil: Franca, Carlos Alberto. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; ArgentinaFil: Guida, Jorge Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química; ArgentinaPergamon-Elsevier Science Ltd2017-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/255695Chacón Villalba, Elizabeth; Franca, Carlos Alberto; Guida, Jorge Alberto; 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; Pergamon-Elsevier Science Ltd; Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy; 176; 1-2017; 189-1961386-1425CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.saa.2017.01.003info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:17:13Zoai:ri.conicet.gov.ar:11336/255695instacron: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 10:17:13.968CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
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, Elizabeth
NITROUS OXIDE COMPLEXES
HYPONITRITE
COBALT BINUCLEAR COMPLEX
SOLID STATE PHOTOLYSIS
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, Elizabeth
Franca, Carlos Alberto
Guida, Jorge Alberto
author Chacón Villalba, Elizabeth
author_facet Chacón Villalba, Elizabeth
Franca, Carlos Alberto
Guida, Jorge Alberto
author_role author
author2 Franca, Carlos Alberto
Guida, Jorge Alberto
author2_role author
author
dc.subject.none.fl_str_mv NITROUS OXIDE COMPLEXES
HYPONITRITE
COBALT BINUCLEAR COMPLEX
SOLID STATE PHOTOLYSIS
topic NITROUS OXIDE COMPLEXES
HYPONITRITE
COBALT BINUCLEAR COMPLEX
SOLID STATE PHOTOLYSIS
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The solid state photolysis of sodium, silver and thallium hyponitrite (M 2 N 2 O 2 , M = Na, Ag, Tl) salts and abinuclear complex of cobalt bridged by hyponitrite ([Co(NH 3 ) 5 -N(O)-NO-Co(NH 3 ) 5 ] 4+ ) were studied by irradi-ation with visible and UV light in the electronic absorption region. The UV?visible spectra for free hyponitrite ionand binuclear complex of cobalt were interpreted in terms of Density Functional Theory calculations in order toexplain photolysis behavior.The photolysis of each compound depends selectively on the irradiation wavelength. Irradiation with340?460 nm light and with the 488 nm laser line generates photolysis only in silver and thalliumhyponitrite salts, while 253.7 nm light photolyzed all the studied compounds.Infrared spectroscopy was used to follow the photolysis process and to identify the generated products. Remark-ably, gaseous N 2 O was detected after photolysis in the infrared spectra of sodium, silver, and thallium hyponitriteKBr pellets. The spectra for [Co(NH 3 ) 5 -N(O)-NO-Co(NH 3 ) 5 ] 4+ suggest that one cobalt ion remains bonded to N 2 Ofrom which the generation of a [(NH 3 ) 5 CoNNO] +3 complex is inferred. Density Functional Theory (DFT) basedcalculations confirm the stability of this last complex and provide the theoretical data which are used in the in-terpretation of the electronic spectra of the hyponitrite ion and the cobalt binuclear complex and thus in the elu-cidation of their photolysis behavior.Carbonate ion is also detected after photolysis in all studied compounds, presumably due to the reaction of atmo-spheric CO 2 with the microcrystal surface reaction products. Kinetic measurements for the photolysis of thebinuclear complex suggest a first order law for the intensity decay of the hyponitrite IR bands and for the inten-sity increase in the N 2 O generation. Predicted and experimental data are in very good agreement.
Fil: Chacón Villalba, Elizabeth. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Franca, Carlos Alberto. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Guida, Jorge Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química; Argentina
description The solid state photolysis of sodium, silver and thallium hyponitrite (M 2 N 2 O 2 , M = Na, Ag, Tl) salts and abinuclear complex of cobalt bridged by hyponitrite ([Co(NH 3 ) 5 -N(O)-NO-Co(NH 3 ) 5 ] 4+ ) were studied by irradi-ation with visible and UV light in the electronic absorption region. The UV?visible spectra for free hyponitrite ionand binuclear complex of cobalt were interpreted in terms of Density Functional Theory calculations in order toexplain photolysis behavior.The photolysis of each compound depends selectively on the irradiation wavelength. Irradiation with340?460 nm light and with the 488 nm laser line generates photolysis only in silver and thalliumhyponitrite salts, while 253.7 nm light photolyzed all the studied compounds.Infrared spectroscopy was used to follow the photolysis process and to identify the generated products. Remark-ably, gaseous N 2 O was detected after photolysis in the infrared spectra of sodium, silver, and thallium hyponitriteKBr pellets. The spectra for [Co(NH 3 ) 5 -N(O)-NO-Co(NH 3 ) 5 ] 4+ suggest that one cobalt ion remains bonded to N 2 Ofrom which the generation of a [(NH 3 ) 5 CoNNO] +3 complex is inferred. Density Functional Theory (DFT) basedcalculations confirm the stability of this last complex and provide the theoretical data which are used in the in-terpretation of the electronic spectra of the hyponitrite ion and the cobalt binuclear complex and thus in the elu-cidation of their photolysis behavior.Carbonate ion is also detected after photolysis in all studied compounds, presumably due to the reaction of atmo-spheric CO 2 with the microcrystal surface reaction products. Kinetic measurements for the photolysis of thebinuclear complex suggest a first order law for the intensity decay of the hyponitrite IR bands and for the inten-sity increase in the N 2 O generation. Predicted and experimental data are in very good agreement.
publishDate 2017
dc.date.none.fl_str_mv 2017-01
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/11336/255695
Chacón Villalba, Elizabeth; Franca, Carlos Alberto; Guida, Jorge Alberto; 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; Pergamon-Elsevier Science Ltd; Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy; 176; 1-2017; 189-196
1386-1425
CONICET Digital
CONICET
url http://hdl.handle.net/11336/255695
identifier_str_mv Chacón Villalba, Elizabeth; Franca, Carlos Alberto; Guida, Jorge Alberto; 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; Pergamon-Elsevier Science Ltd; Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy; 176; 1-2017; 189-196
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/doi/10.1016/j.saa.2017.01.003
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
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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