New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl2: Influence of O2 and comparison with gas-phase photochemistry
- 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.
Fil: Tamone, Luciana Mariel. 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
Fil: Picone, Andrea Lorena. 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
Fil: Romano, Rosana Mariel. 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
-
DICHLOROACETYL CHLORIDE
DIMERS
IR SPECTROSCOPY
MATRIX-ISOLATION
PHOTOCHEMISTRY - Nivel de accesibilidad
- acceso abierto
- Condiciones de uso
- https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
- Repositorio
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/180766
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New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl2: Influence of O2 and comparison with gas-phase photochemistryTamone, Luciana MarielPicone, Andrea LorenaRomano, Rosana MarielDICHLOROACETYL CHLORIDEDIMERSIR SPECTROSCOPYMATRIX-ISOLATIONPHOTOCHEMISTRYhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Photolysis 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.Fil: Tamone, Luciana Mariel. 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; ArgentinaFil: Picone, Andrea Lorena. 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; ArgentinaFil: Romano, Rosana Mariel. 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; ArgentinaElsevier Science2021-06info: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/11336/180766Tamone, Luciana Mariel; Picone, Andrea Lorena; Romano, Rosana Mariel; New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl2: Influence of O2 and comparison with gas-phase photochemistry; Elsevier Science; Journal of Photochemistry and Photobiology; 6; 100019; 6-2021; 1-102666-4690CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S266646902100004Xinfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.jpap.2021.100019info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:08:34Zoai:ri.conicet.gov.ar:11336/180766instacron: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:34982025-09-03 10:08:34.781CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse |
dc.title.none.fl_str_mv |
New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl2: Influence of O2 and comparison with gas-phase photochemistry |
title |
New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl2: Influence of O2 and comparison with gas-phase photochemistry |
spellingShingle |
New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl2: Influence of O2 and comparison with gas-phase photochemistry Tamone, Luciana Mariel DICHLOROACETYL CHLORIDE DIMERS IR SPECTROSCOPY MATRIX-ISOLATION PHOTOCHEMISTRY |
title_short |
New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl2: Influence of O2 and comparison with gas-phase photochemistry |
title_full |
New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl2: Influence of O2 and comparison with gas-phase photochemistry |
title_fullStr |
New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl2: Influence of O2 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)CHCl2: Influence of O2 and comparison with gas-phase photochemistry |
title_sort |
New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl2: Influence of O2 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 |
DICHLOROACETYL CHLORIDE DIMERS IR SPECTROSCOPY MATRIX-ISOLATION PHOTOCHEMISTRY |
topic |
DICHLOROACETYL CHLORIDE DIMERS IR SPECTROSCOPY MATRIX-ISOLATION PHOTOCHEMISTRY |
purl_subject.fl_str_mv |
https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
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. Fil: Tamone, Luciana Mariel. 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 Fil: Picone, Andrea Lorena. 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 Fil: Romano, Rosana Mariel. 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 |
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 |
2021-06 |
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/11336/180766 Tamone, Luciana Mariel; Picone, Andrea Lorena; Romano, Rosana Mariel; New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl2: Influence of O2 and comparison with gas-phase photochemistry; Elsevier Science; Journal of Photochemistry and Photobiology; 6; 100019; 6-2021; 1-10 2666-4690 CONICET Digital CONICET |
url |
http://hdl.handle.net/11336/180766 |
identifier_str_mv |
Tamone, Luciana Mariel; Picone, Andrea Lorena; Romano, Rosana Mariel; New insights into the Ar-matrix-isolation FTIR spectroscopy and photochemistry of dichloroacetyl chloride, ClC(O)CHCl2: Influence of O2 and comparison with gas-phase photochemistry; Elsevier Science; Journal of Photochemistry and Photobiology; 6; 100019; 6-2021; 1-10 2666-4690 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/S266646902100004X info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jpap.2021.100019 |
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 application/pdf application/pdf |
dc.publisher.none.fl_str_mv |
Elsevier Science |
publisher.none.fl_str_mv |
Elsevier Science |
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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1842270050233352192 |
score |
13.13397 |