The role of Tris(2-carboxyethyl)phosphine reducing agent in the controlled formation of α,ω-Alkanedithiols Monolayers on Au(111) with monocoordinated and bicoordinated configuratio...

Autores
Euti, Esteban; Velez, Patricio; Leiva, Ezequiel Pedro Marcos; Macagno, Vicente Antonio; Paredes Olivera, Patricia; Patrito, Eduardo Martin; Cometto, Fernando Pablo
Año de publicación
2016
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The addition of the reducing agent tris(2-carboxyethyl) phosphine (TCEP) during the formation of α,ω-alkanedithiols monolayers on Au(111) using the immersion method produces the assembly of monolayers with bicoordinated molecules (both S-terminal groups bound to the surface) that have a reductive desorption potential that is more positive than for monolayers with monocoordinated molecules in a standing up configuration. We show that the use of TCEP either during formation of the monolayer or as a post treatment procedure allows the controlled formation of monolayers with bicoordinated or monocoordinated configurations. Density Functional Theory (DFT) calculations were performed to elucidate the role of TCEP in the formation of the bicoordinated configuration. We investigated the TCEP-dithiol interaction in ethanol solvent as well as the coadsorption of trimethylphosphine with 1,2-ethanedithiol on Au(111). The Brønsted base character of the phosphine facilitates the H exchange from the −SHgroups of the dithiol to the phosphorous atom of TCEP with very low activation energy barriers, thus allowing the thiolate groups to bind to the Au(111) surface, thus yielding the bicoordinated configuration. Dithiol lifting mechanisms such as H exchange between S atoms and the formation of intra/inter layer disulfide bonds have much higher energy barriers.
Fil: Euti, Esteban. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Velez, Patricio. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Matemática y Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Leiva, Ezequiel Pedro Marcos. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Matemática y Física; Argentina
Fil: Macagno, Vicente Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Paredes Olivera, Patricia. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Matemática y Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Patrito, Eduardo Martin. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Cometto, Fernando Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Materia
ALKANEDITHIOS
TCEP
AU (111)
REDUCTIVE DESORPTION
DFT
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/23986
Acceder
id CONICETDig_e43a5972ac68f7f07363d618039ee453
oai_identifier_str oai:ri.conicet.gov.ar:11336/23986
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling The role of Tris(2-carboxyethyl)phosphine reducing agent in the controlled formation of α,ω-Alkanedithiols Monolayers on Au(111) with monocoordinated and bicoordinated configurationsEuti, EstebanVelez, PatricioLeiva, Ezequiel Pedro MarcosMacagno, Vicente AntonioParedes Olivera, PatriciaPatrito, Eduardo MartinCometto, Fernando PabloALKANEDITHIOSTCEPAU (111)REDUCTIVE DESORPTIONDFThttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The addition of the reducing agent tris(2-carboxyethyl) phosphine (TCEP) during the formation of α,ω-alkanedithiols monolayers on Au(111) using the immersion method produces the assembly of monolayers with bicoordinated molecules (both S-terminal groups bound to the surface) that have a reductive desorption potential that is more positive than for monolayers with monocoordinated molecules in a standing up configuration. We show that the use of TCEP either during formation of the monolayer or as a post treatment procedure allows the controlled formation of monolayers with bicoordinated or monocoordinated configurations. Density Functional Theory (DFT) calculations were performed to elucidate the role of TCEP in the formation of the bicoordinated configuration. We investigated the TCEP-dithiol interaction in ethanol solvent as well as the coadsorption of trimethylphosphine with 1,2-ethanedithiol on Au(111). The Brønsted base character of the phosphine facilitates the H exchange from the −SHgroups of the dithiol to the phosphorous atom of TCEP with very low activation energy barriers, thus allowing the thiolate groups to bind to the Au(111) surface, thus yielding the bicoordinated configuration. Dithiol lifting mechanisms such as H exchange between S atoms and the formation of intra/inter layer disulfide bonds have much higher energy barriers.Fil: Euti, Esteban. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Velez, Patricio. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Matemática y Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Leiva, Ezequiel Pedro Marcos. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Matemática y Física; ArgentinaFil: Macagno, Vicente Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Paredes Olivera, Patricia. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Matemática y Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Patrito, Eduardo Martin. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Cometto, Fernando Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaAmerican Chemical Society2016-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/23986Euti, Esteban; Velez, Patricio; Leiva, Ezequiel Pedro Marcos; Macagno, Vicente Antonio; Paredes Olivera, Patricia; et al.; The role of Tris(2-carboxyethyl)phosphine reducing agent in the controlled formation of α,ω-Alkanedithiols Monolayers on Au(111) with monocoordinated and bicoordinated configurations; American Chemical Society; Langmuir; 32; 37; 8-2016; 9428-94360743-74631520-5827CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/acs.langmuir.6b02079info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/acs.langmuir.6b02079info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:55:50Zoai:ri.conicet.gov.ar:11336/23986instacron: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 09:55:50.655CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv The role of Tris(2-carboxyethyl)phosphine reducing agent in the controlled formation of α,ω-Alkanedithiols Monolayers on Au(111) with monocoordinated and bicoordinated configurations
title The role of Tris(2-carboxyethyl)phosphine reducing agent in the controlled formation of α,ω-Alkanedithiols Monolayers on Au(111) with monocoordinated and bicoordinated configurations
spellingShingle The role of Tris(2-carboxyethyl)phosphine reducing agent in the controlled formation of α,ω-Alkanedithiols Monolayers on Au(111) with monocoordinated and bicoordinated configurations
Euti, Esteban
ALKANEDITHIOS
TCEP
AU (111)
REDUCTIVE DESORPTION
DFT
title_short The role of Tris(2-carboxyethyl)phosphine reducing agent in the controlled formation of α,ω-Alkanedithiols Monolayers on Au(111) with monocoordinated and bicoordinated configurations
title_full The role of Tris(2-carboxyethyl)phosphine reducing agent in the controlled formation of α,ω-Alkanedithiols Monolayers on Au(111) with monocoordinated and bicoordinated configurations
title_fullStr The role of Tris(2-carboxyethyl)phosphine reducing agent in the controlled formation of α,ω-Alkanedithiols Monolayers on Au(111) with monocoordinated and bicoordinated configurations
title_full_unstemmed The role of Tris(2-carboxyethyl)phosphine reducing agent in the controlled formation of α,ω-Alkanedithiols Monolayers on Au(111) with monocoordinated and bicoordinated configurations
title_sort The role of Tris(2-carboxyethyl)phosphine reducing agent in the controlled formation of α,ω-Alkanedithiols Monolayers on Au(111) with monocoordinated and bicoordinated configurations
dc.creator.none.fl_str_mv Euti, Esteban
Velez, Patricio
Leiva, Ezequiel Pedro Marcos
Macagno, Vicente Antonio
Paredes Olivera, Patricia
Patrito, Eduardo Martin
Cometto, Fernando Pablo
author Euti, Esteban
author_facet Euti, Esteban
Velez, Patricio
Leiva, Ezequiel Pedro Marcos
Macagno, Vicente Antonio
Paredes Olivera, Patricia
Patrito, Eduardo Martin
Cometto, Fernando Pablo
author_role author
author2 Velez, Patricio
Leiva, Ezequiel Pedro Marcos
Macagno, Vicente Antonio
Paredes Olivera, Patricia
Patrito, Eduardo Martin
Cometto, Fernando Pablo
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv ALKANEDITHIOS
TCEP
AU (111)
REDUCTIVE DESORPTION
DFT
topic ALKANEDITHIOS
TCEP
AU (111)
REDUCTIVE DESORPTION
DFT
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 addition of the reducing agent tris(2-carboxyethyl) phosphine (TCEP) during the formation of α,ω-alkanedithiols monolayers on Au(111) using the immersion method produces the assembly of monolayers with bicoordinated molecules (both S-terminal groups bound to the surface) that have a reductive desorption potential that is more positive than for monolayers with monocoordinated molecules in a standing up configuration. We show that the use of TCEP either during formation of the monolayer or as a post treatment procedure allows the controlled formation of monolayers with bicoordinated or monocoordinated configurations. Density Functional Theory (DFT) calculations were performed to elucidate the role of TCEP in the formation of the bicoordinated configuration. We investigated the TCEP-dithiol interaction in ethanol solvent as well as the coadsorption of trimethylphosphine with 1,2-ethanedithiol on Au(111). The Brønsted base character of the phosphine facilitates the H exchange from the −SHgroups of the dithiol to the phosphorous atom of TCEP with very low activation energy barriers, thus allowing the thiolate groups to bind to the Au(111) surface, thus yielding the bicoordinated configuration. Dithiol lifting mechanisms such as H exchange between S atoms and the formation of intra/inter layer disulfide bonds have much higher energy barriers.
Fil: Euti, Esteban. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Velez, Patricio. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Matemática y Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Leiva, Ezequiel Pedro Marcos. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Matemática y Física; Argentina
Fil: Macagno, Vicente Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Paredes Olivera, Patricia. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Matemática y Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Patrito, Eduardo Martin. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Cometto, Fernando Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
description The addition of the reducing agent tris(2-carboxyethyl) phosphine (TCEP) during the formation of α,ω-alkanedithiols monolayers on Au(111) using the immersion method produces the assembly of monolayers with bicoordinated molecules (both S-terminal groups bound to the surface) that have a reductive desorption potential that is more positive than for monolayers with monocoordinated molecules in a standing up configuration. We show that the use of TCEP either during formation of the monolayer or as a post treatment procedure allows the controlled formation of monolayers with bicoordinated or monocoordinated configurations. Density Functional Theory (DFT) calculations were performed to elucidate the role of TCEP in the formation of the bicoordinated configuration. We investigated the TCEP-dithiol interaction in ethanol solvent as well as the coadsorption of trimethylphosphine with 1,2-ethanedithiol on Au(111). The Brønsted base character of the phosphine facilitates the H exchange from the −SHgroups of the dithiol to the phosphorous atom of TCEP with very low activation energy barriers, thus allowing the thiolate groups to bind to the Au(111) surface, thus yielding the bicoordinated configuration. Dithiol lifting mechanisms such as H exchange between S atoms and the formation of intra/inter layer disulfide bonds have much higher energy barriers.
publishDate 2016
dc.date.none.fl_str_mv 2016-08
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/11336/23986
Euti, Esteban; Velez, Patricio; Leiva, Ezequiel Pedro Marcos; Macagno, Vicente Antonio; Paredes Olivera, Patricia; et al.; The role of Tris(2-carboxyethyl)phosphine reducing agent in the controlled formation of α,ω-Alkanedithiols Monolayers on Au(111) with monocoordinated and bicoordinated configurations; American Chemical Society; Langmuir; 32; 37; 8-2016; 9428-9436
0743-7463
1520-5827
CONICET Digital
CONICET
url http://hdl.handle.net/11336/23986
identifier_str_mv Euti, Esteban; Velez, Patricio; Leiva, Ezequiel Pedro Marcos; Macagno, Vicente Antonio; Paredes Olivera, Patricia; et al.; The role of Tris(2-carboxyethyl)phosphine reducing agent in the controlled formation of α,ω-Alkanedithiols Monolayers on Au(111) with monocoordinated and bicoordinated configurations; American Chemical Society; Langmuir; 32; 37; 8-2016; 9428-9436
0743-7463
1520-5827
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.langmuir.6b02079
info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/acs.langmuir.6b02079
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
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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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score 13.070432

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