Ubiquitous deprotonation of terephthalic acid in the self-assembled phases on Cu(100)

Autores
Quiroga Argañaraz, Maria Bernarda; Cristina, Lucila Josefina; Parra Rodríguez, Laura María; Cossaro, A.; Verdini, A.; Floreano, L.; Fuhr, Javier Daniel; Gayone, Julio Esteban; Ascolani, Hugo del Lujan
Año de publicación
2018
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We performed an exhaustive study of terephthalic acid (TPA) self-assembly on a Cu(100) surface, where first-layer molecules display two sequential phase transitions in the 200-400 K temperature range, corresponding to different stages of molecular deprotonation. We followed the chemical and structural changes by means of high-resolution X-ray photoelectron spectroscopy (XPS) and variable-temperature scanning tunneling microscopy (STM), which were interpreted on the basis of density functional theory (DFT) calculations and photoemission simulations. In order to reveal the spectroscopic contributions of the molecules in different states of deprotonation, we modified the substrate reactivity by deposition of a small amount of Sn, which hampers the deprotonation reaction. We found that the characteristic molecular ribbons of the TPA/Cu(100) α-phase at a low temperature contain a significant fraction of partially deprotonated molecules, in contrast to the expectation of a fully protonated phase, where the self-assembly was claimed to be simply driven by the intermolecular double hydrogen bonds [OH⋯O]. On the basis of our simulations, we propose a model where the carboxylate groups of the partially deprotonated molecules form single hydrogen bonds with the carboxylic groups of the fully protonated molecules. Using real time XPS, we also monitored the kinetics of the deprotonation reaction. We show that the network of mixed single and double hydrogen bonds inhibits further deprotonation up to ∼270 K, whereas the isolated molecules display a much lower deprotonation barrier.
Fil: Quiroga Argañaraz, Maria Bernarda. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina
Fil: Cristina, Lucila Josefina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; Argentina
Fil: Parra Rodríguez, Laura María. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina
Fil: Cossaro, A.. Consiglio Nazionale delle Ricerche; Italia
Fil: Verdini, A.. Consiglio Nazionale delle Ricerche; Italia
Fil: Floreano, L.. Consiglio Nazionale delle Ricerche; Italia
Fil: Fuhr, Javier Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina
Fil: Gayone, Julio Esteban. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina
Fil: Ascolani, Hugo del Lujan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina
Materia
TEREPHTHALIC ACID
SELF-ASSEMBLY
CU(100)
SURFACES
TEREPHTHALIC ACID
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:11336/86984
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/86984
network_acronym_str CONICETDig
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network_name_str CONICET Digital (CONICET)
spelling Ubiquitous deprotonation of terephthalic acid in the self-assembled phases on Cu(100)Quiroga Argañaraz, Maria BernardaCristina, Lucila JosefinaParra Rodríguez, Laura MaríaCossaro, A.Verdini, A.Floreano, L.Fuhr, Javier DanielGayone, Julio EstebanAscolani, Hugo del LujanTEREPHTHALIC ACIDSELF-ASSEMBLYCU(100)SURFACESTEREPHTHALIC ACIDhttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1We performed an exhaustive study of terephthalic acid (TPA) self-assembly on a Cu(100) surface, where first-layer molecules display two sequential phase transitions in the 200-400 K temperature range, corresponding to different stages of molecular deprotonation. We followed the chemical and structural changes by means of high-resolution X-ray photoelectron spectroscopy (XPS) and variable-temperature scanning tunneling microscopy (STM), which were interpreted on the basis of density functional theory (DFT) calculations and photoemission simulations. In order to reveal the spectroscopic contributions of the molecules in different states of deprotonation, we modified the substrate reactivity by deposition of a small amount of Sn, which hampers the deprotonation reaction. We found that the characteristic molecular ribbons of the TPA/Cu(100) α-phase at a low temperature contain a significant fraction of partially deprotonated molecules, in contrast to the expectation of a fully protonated phase, where the self-assembly was claimed to be simply driven by the intermolecular double hydrogen bonds [OH⋯O]. On the basis of our simulations, we propose a model where the carboxylate groups of the partially deprotonated molecules form single hydrogen bonds with the carboxylic groups of the fully protonated molecules. Using real time XPS, we also monitored the kinetics of the deprotonation reaction. We show that the network of mixed single and double hydrogen bonds inhibits further deprotonation up to ∼270 K, whereas the isolated molecules display a much lower deprotonation barrier.Fil: Quiroga Argañaraz, Maria Bernarda. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; ArgentinaFil: Cristina, Lucila Josefina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; ArgentinaFil: Parra Rodríguez, Laura María. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; ArgentinaFil: Cossaro, A.. Consiglio Nazionale delle Ricerche; ItaliaFil: Verdini, A.. Consiglio Nazionale delle Ricerche; ItaliaFil: Floreano, L.. Consiglio Nazionale delle Ricerche; ItaliaFil: Fuhr, Javier Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; ArgentinaFil: Gayone, Julio Esteban. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; ArgentinaFil: Ascolani, Hugo del Lujan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; ArgentinaRoyal Society of Chemistry2018-06-09info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/86984Quiroga Argañaraz, Maria Bernarda; Cristina, Lucila Josefina; Parra Rodríguez, Laura María; Cossaro, A.; Verdini, A.; et al.; Ubiquitous deprotonation of terephthalic acid in the self-assembled phases on Cu(100); Royal Society of Chemistry; Physical Chemistry Chemical Physics; 20; 6; 9-6-2018; 4329-43391463-9076CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2018/CP/C7CP06612K#!divAbstractinfo:eu-repo/semantics/altIdentifier/doi/10.1039/C7CP06612Kinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:53:03Zoai:ri.conicet.gov.ar:11336/86984instacron: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:34982025-10-22 11:53:04.187CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Ubiquitous deprotonation of terephthalic acid in the self-assembled phases on Cu(100)
title Ubiquitous deprotonation of terephthalic acid in the self-assembled phases on Cu(100)
spellingShingle Ubiquitous deprotonation of terephthalic acid in the self-assembled phases on Cu(100)
Quiroga Argañaraz, Maria Bernarda
TEREPHTHALIC ACID
SELF-ASSEMBLY
CU(100)
SURFACES
TEREPHTHALIC ACID
title_short Ubiquitous deprotonation of terephthalic acid in the self-assembled phases on Cu(100)
title_full Ubiquitous deprotonation of terephthalic acid in the self-assembled phases on Cu(100)
title_fullStr Ubiquitous deprotonation of terephthalic acid in the self-assembled phases on Cu(100)
title_full_unstemmed Ubiquitous deprotonation of terephthalic acid in the self-assembled phases on Cu(100)
title_sort Ubiquitous deprotonation of terephthalic acid in the self-assembled phases on Cu(100)
dc.creator.none.fl_str_mv Quiroga Argañaraz, Maria Bernarda
Cristina, Lucila Josefina
Parra Rodríguez, Laura María
Cossaro, A.
Verdini, A.
Floreano, L.
Fuhr, Javier Daniel
Gayone, Julio Esteban
Ascolani, Hugo del Lujan
author Quiroga Argañaraz, Maria Bernarda
author_facet Quiroga Argañaraz, Maria Bernarda
Cristina, Lucila Josefina
Parra Rodríguez, Laura María
Cossaro, A.
Verdini, A.
Floreano, L.
Fuhr, Javier Daniel
Gayone, Julio Esteban
Ascolani, Hugo del Lujan
author_role author
author2 Cristina, Lucila Josefina
Parra Rodríguez, Laura María
Cossaro, A.
Verdini, A.
Floreano, L.
Fuhr, Javier Daniel
Gayone, Julio Esteban
Ascolani, Hugo del Lujan
author2_role author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv TEREPHTHALIC ACID
SELF-ASSEMBLY
CU(100)
SURFACES
TEREPHTHALIC ACID
topic TEREPHTHALIC ACID
SELF-ASSEMBLY
CU(100)
SURFACES
TEREPHTHALIC ACID
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv We performed an exhaustive study of terephthalic acid (TPA) self-assembly on a Cu(100) surface, where first-layer molecules display two sequential phase transitions in the 200-400 K temperature range, corresponding to different stages of molecular deprotonation. We followed the chemical and structural changes by means of high-resolution X-ray photoelectron spectroscopy (XPS) and variable-temperature scanning tunneling microscopy (STM), which were interpreted on the basis of density functional theory (DFT) calculations and photoemission simulations. In order to reveal the spectroscopic contributions of the molecules in different states of deprotonation, we modified the substrate reactivity by deposition of a small amount of Sn, which hampers the deprotonation reaction. We found that the characteristic molecular ribbons of the TPA/Cu(100) α-phase at a low temperature contain a significant fraction of partially deprotonated molecules, in contrast to the expectation of a fully protonated phase, where the self-assembly was claimed to be simply driven by the intermolecular double hydrogen bonds [OH⋯O]. On the basis of our simulations, we propose a model where the carboxylate groups of the partially deprotonated molecules form single hydrogen bonds with the carboxylic groups of the fully protonated molecules. Using real time XPS, we also monitored the kinetics of the deprotonation reaction. We show that the network of mixed single and double hydrogen bonds inhibits further deprotonation up to ∼270 K, whereas the isolated molecules display a much lower deprotonation barrier.
Fil: Quiroga Argañaraz, Maria Bernarda. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina
Fil: Cristina, Lucila Josefina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; Argentina
Fil: Parra Rodríguez, Laura María. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina
Fil: Cossaro, A.. Consiglio Nazionale delle Ricerche; Italia
Fil: Verdini, A.. Consiglio Nazionale delle Ricerche; Italia
Fil: Floreano, L.. Consiglio Nazionale delle Ricerche; Italia
Fil: Fuhr, Javier Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina
Fil: Gayone, Julio Esteban. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina
Fil: Ascolani, Hugo del Lujan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina
description We performed an exhaustive study of terephthalic acid (TPA) self-assembly on a Cu(100) surface, where first-layer molecules display two sequential phase transitions in the 200-400 K temperature range, corresponding to different stages of molecular deprotonation. We followed the chemical and structural changes by means of high-resolution X-ray photoelectron spectroscopy (XPS) and variable-temperature scanning tunneling microscopy (STM), which were interpreted on the basis of density functional theory (DFT) calculations and photoemission simulations. In order to reveal the spectroscopic contributions of the molecules in different states of deprotonation, we modified the substrate reactivity by deposition of a small amount of Sn, which hampers the deprotonation reaction. We found that the characteristic molecular ribbons of the TPA/Cu(100) α-phase at a low temperature contain a significant fraction of partially deprotonated molecules, in contrast to the expectation of a fully protonated phase, where the self-assembly was claimed to be simply driven by the intermolecular double hydrogen bonds [OH⋯O]. On the basis of our simulations, we propose a model where the carboxylate groups of the partially deprotonated molecules form single hydrogen bonds with the carboxylic groups of the fully protonated molecules. Using real time XPS, we also monitored the kinetics of the deprotonation reaction. We show that the network of mixed single and double hydrogen bonds inhibits further deprotonation up to ∼270 K, whereas the isolated molecules display a much lower deprotonation barrier.
publishDate 2018
dc.date.none.fl_str_mv 2018-06-09
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/11336/86984
Quiroga Argañaraz, Maria Bernarda; Cristina, Lucila Josefina; Parra Rodríguez, Laura María; Cossaro, A.; Verdini, A.; et al.; Ubiquitous deprotonation of terephthalic acid in the self-assembled phases on Cu(100); Royal Society of Chemistry; Physical Chemistry Chemical Physics; 20; 6; 9-6-2018; 4329-4339
1463-9076
CONICET Digital
CONICET
url http://hdl.handle.net/11336/86984
identifier_str_mv Quiroga Argañaraz, Maria Bernarda; Cristina, Lucila Josefina; Parra Rodríguez, Laura María; Cossaro, A.; Verdini, A.; et al.; Ubiquitous deprotonation of terephthalic acid in the self-assembled phases on Cu(100); Royal Society of Chemistry; Physical Chemistry Chemical Physics; 20; 6; 9-6-2018; 4329-4339
1463-9076
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://pubs.rsc.org/en/content/articlelanding/2018/CP/C7CP06612K#!divAbstract
info:eu-repo/semantics/altIdentifier/doi/10.1039/C7CP06612K
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
application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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 12.982451

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