New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl<SUB>2</SUB>: Influence of O<SUB>2</SUB> and comparison with ga...

Autores
Tamone, Luciana Mariel; Picone, Andrea Lorena; Romano, Rosana Mariel
Año de publicación
2021
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Photolysis products of dichloroacetyl chloride (DCAC) isolated in Ar matrix and in gas phase, in the absence and presence of molecular oxygen, were studied by means of FTIR spectroscopy. The samples were exposed to light of different energy ranges (200-800, 280-320, 350-450 and 400-800 nm). DCAC is photostable when irradiated with light of wavelengths above 400 nm, and gives dichloroketene after photolysis with light between 280-320 and 350-450 nm. Exposure of DCAC to broad-band radiation (200-800 nm) produces dichloroketene as an intermediate photoproduct, and different 1:1 CHCl3:CO molecular complexes after further irradiation. HCl, CO and CHCl3 were detected in gas-phase DCAC photolysis. ClC(O)CCl2CCl2H molecule was also proposed, in a mechanism that involve the insertion of :CCl2 biradical into the CC bond of DCAC. The photochemical reaction of DCAC with O2 in Ar matrix gives Cl2CO and CO2. The same photoproducts, together with HCl, were observed in the gas-phase photochemical reaction. Additionally, the FTIR spectra of DCAC isolated in solid Ar were fully interpreted in terms of an equilibrium between syn (the HC bond syn with respect to the CO bond) and gauche conformers. Some absorptions, which grow as the DCAC:Ar ratio increases, were attributed to dimeric forms. The most stable dimer was predicted by DFT calculations as composed by two DCAC molecules with syn conformations, interacting through two H-bonds in a structure with Ci symmetry.
Centro de Química Inorgánica
Materia
Química
Dichloroacetyl chloride
Matrix-isolation
Photochemistry
IR spectroscopy
Dimers
Nivel de accesibilidad
acceso abierto
Condiciones de uso
http://creativecommons.org/licenses/by-nc-nd/4.0/
Repositorio
SEDICI (UNLP)
Institución
Universidad Nacional de La Plata
OAI Identificador
oai:sedici.unlp.edu.ar:10915/112819

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spelling New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl<SUB>2</SUB>: Influence of O<SUB>2</SUB> and comparison with gas-phase photochemistryTamone, Luciana MarielPicone, Andrea LorenaRomano, Rosana MarielQuímicaDichloroacetyl chlorideMatrix-isolationPhotochemistryIR spectroscopyDimersPhotolysis products of dichloroacetyl chloride (DCAC) isolated in Ar matrix and in gas phase, in the absence and presence of molecular oxygen, were studied by means of FTIR spectroscopy. The samples were exposed to light of different energy ranges (200-800, 280-320, 350-450 and 400-800 nm). DCAC is photostable when irradiated with light of wavelengths above 400 nm, and gives dichloroketene after photolysis with light between 280-320 and 350-450 nm. Exposure of DCAC to broad-band radiation (200-800 nm) produces dichloroketene as an intermediate photoproduct, and different 1:1 CHCl3:CO molecular complexes after further irradiation. HCl, CO and CHCl3 were detected in gas-phase DCAC photolysis. ClC(O)CCl2CCl2H molecule was also proposed, in a mechanism that involve the insertion of :CCl2 biradical into the CC bond of DCAC. The photochemical reaction of DCAC with O2 in Ar matrix gives Cl2CO and CO2. The same photoproducts, together with HCl, were observed in the gas-phase photochemical reaction. Additionally, the FTIR spectra of DCAC isolated in solid Ar were fully interpreted in terms of an equilibrium between syn (the HC bond syn with respect to the CO bond) and gauche conformers. Some absorptions, which grow as the DCAC:Ar ratio increases, were attributed to dimeric forms. The most stable dimer was predicted by DFT calculations as composed by two DCAC molecules with syn conformations, interacting through two H-bonds in a structure with Ci symmetry.Centro de Química Inorgánica2021-01-29info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfhttp://sedici.unlp.edu.ar/handle/10915/112819enginfo:eu-repo/semantics/altIdentifier/issn/2666-4690info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jpap.2021.100019info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-nd/4.0/Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)reponame:SEDICI (UNLP)instname:Universidad Nacional de La Platainstacron:UNLP2025-09-03T10:58:06Zoai:sedici.unlp.edu.ar:10915/112819Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292025-09-03 10:58:06.776SEDICI (UNLP) - Universidad Nacional de La Platafalse
dc.title.none.fl_str_mv New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl<SUB>2</SUB>: Influence of O<SUB>2</SUB> and comparison with gas-phase photochemistry
title New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl<SUB>2</SUB>: Influence of O<SUB>2</SUB> and comparison with gas-phase photochemistry
spellingShingle New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl<SUB>2</SUB>: Influence of O<SUB>2</SUB> and comparison with gas-phase photochemistry
Tamone, Luciana Mariel
Química
Dichloroacetyl chloride
Matrix-isolation
Photochemistry
IR spectroscopy
Dimers
title_short New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl<SUB>2</SUB>: Influence of O<SUB>2</SUB> and comparison with gas-phase photochemistry
title_full New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl<SUB>2</SUB>: Influence of O<SUB>2</SUB> and comparison with gas-phase photochemistry
title_fullStr New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl<SUB>2</SUB>: Influence of O<SUB>2</SUB> and comparison with gas-phase photochemistry
title_full_unstemmed New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl<SUB>2</SUB>: Influence of O<SUB>2</SUB> and comparison with gas-phase photochemistry
title_sort New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl<SUB>2</SUB>: Influence of O<SUB>2</SUB> and comparison with gas-phase photochemistry
dc.creator.none.fl_str_mv Tamone, Luciana Mariel
Picone, Andrea Lorena
Romano, Rosana Mariel
author Tamone, Luciana Mariel
author_facet Tamone, Luciana Mariel
Picone, Andrea Lorena
Romano, Rosana Mariel
author_role author
author2 Picone, Andrea Lorena
Romano, Rosana Mariel
author2_role author
author
dc.subject.none.fl_str_mv Química
Dichloroacetyl chloride
Matrix-isolation
Photochemistry
IR spectroscopy
Dimers
topic Química
Dichloroacetyl chloride
Matrix-isolation
Photochemistry
IR spectroscopy
Dimers
dc.description.none.fl_txt_mv Photolysis products of dichloroacetyl chloride (DCAC) isolated in Ar matrix and in gas phase, in the absence and presence of molecular oxygen, were studied by means of FTIR spectroscopy. The samples were exposed to light of different energy ranges (200-800, 280-320, 350-450 and 400-800 nm). DCAC is photostable when irradiated with light of wavelengths above 400 nm, and gives dichloroketene after photolysis with light between 280-320 and 350-450 nm. Exposure of DCAC to broad-band radiation (200-800 nm) produces dichloroketene as an intermediate photoproduct, and different 1:1 CHCl3:CO molecular complexes after further irradiation. HCl, CO and CHCl3 were detected in gas-phase DCAC photolysis. ClC(O)CCl2CCl2H molecule was also proposed, in a mechanism that involve the insertion of :CCl2 biradical into the CC bond of DCAC. The photochemical reaction of DCAC with O2 in Ar matrix gives Cl2CO and CO2. The same photoproducts, together with HCl, were observed in the gas-phase photochemical reaction. Additionally, the FTIR spectra of DCAC isolated in solid Ar were fully interpreted in terms of an equilibrium between syn (the HC bond syn with respect to the CO bond) and gauche conformers. Some absorptions, which grow as the DCAC:Ar ratio increases, were attributed to dimeric forms. The most stable dimer was predicted by DFT calculations as composed by two DCAC molecules with syn conformations, interacting through two H-bonds in a structure with Ci symmetry.
Centro de Química Inorgánica
description Photolysis products of dichloroacetyl chloride (DCAC) isolated in Ar matrix and in gas phase, in the absence and presence of molecular oxygen, were studied by means of FTIR spectroscopy. The samples were exposed to light of different energy ranges (200-800, 280-320, 350-450 and 400-800 nm). DCAC is photostable when irradiated with light of wavelengths above 400 nm, and gives dichloroketene after photolysis with light between 280-320 and 350-450 nm. Exposure of DCAC to broad-band radiation (200-800 nm) produces dichloroketene as an intermediate photoproduct, and different 1:1 CHCl3:CO molecular complexes after further irradiation. HCl, CO and CHCl3 were detected in gas-phase DCAC photolysis. ClC(O)CCl2CCl2H molecule was also proposed, in a mechanism that involve the insertion of :CCl2 biradical into the CC bond of DCAC. The photochemical reaction of DCAC with O2 in Ar matrix gives Cl2CO and CO2. The same photoproducts, together with HCl, were observed in the gas-phase photochemical reaction. Additionally, the FTIR spectra of DCAC isolated in solid Ar were fully interpreted in terms of an equilibrium between syn (the HC bond syn with respect to the CO bond) and gauche conformers. Some absorptions, which grow as the DCAC:Ar ratio increases, were attributed to dimeric forms. The most stable dimer was predicted by DFT calculations as composed by two DCAC molecules with syn conformations, interacting through two H-bonds in a structure with Ci symmetry.
publishDate 2021
dc.date.none.fl_str_mv 2021-01-29
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
Articulo
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://sedici.unlp.edu.ar/handle/10915/112819
url http://sedici.unlp.edu.ar/handle/10915/112819
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/issn/2666-4690
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jpap.2021.100019
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-nd/4.0/
Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-nd/4.0/
Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)
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