Unlocking the Fluorine‐Free Buoy Effect: Surface‐Enriched Ruthenium Polypyridine Complexes in Ionic Liquids

Autores
Sanchez Merlinsky, Luciano; Hemmeter, Daniel; Baraldo Victorica, Luis Mario; Maier, Florian; Steinruck, Hans Peter; Williams, Federico José
Año de publicación
2024
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Controlling the local concentration of metal complexes at the surface of ionic liquids (ILs) is a highly sought-after objective due to its pivotal implications in supported ionic liquid phase (SILP) catalysis. Equally important is to avoid per- and polyfluorinated substances due to environmental concerns. Herein, we investigate the surface enrichment of Ru polypyridyl complexes with fluorine-free alkylic side groups of varying lengths and shapes, using the hydrophilic IL [C2C1Im][OAc] as solvent. Additional charged carboxylate groups are included into the polypyridyl ligands to increase the solubility of the complex in the IL. When the ligand system is functionalized with long and hydrophobic alkyl side chains, the complex predominantly localizes at the IL/vacuum interface, as deduced from angle-resolved X-ray photoelectron spectroscopy. Conversely, in the presence of short or more bulky substituents, no surface enrichment is observed. This buoy-like behaviour with fluorine-free side groups is explored for 0.05 %mol to 1 %mol solutions. Intriguingly, surface saturation occurs at approximately 0.5 %mol, which is beneficial to the efficient operation of catalytic systems featuring high surface areas, such as SILP catalysts.
Fil: Sanchez Merlinsky, Luciano. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Hemmeter, Daniel. Universitat Erlangen Nuremberg; Alemania
Fil: Baraldo Victorica, Luis Mario. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Maier, Florian. Universitat Erlangen Nuremberg; Alemania
Fil: Steinruck, Hans Peter. Universitat Erlangen Nuremberg; Alemania
Fil: Williams, Federico José. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Materia
Ru polypyridine
ionic liquid
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/262187
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/262187
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Unlocking the Fluorine‐Free Buoy Effect: Surface‐Enriched Ruthenium Polypyridine Complexes in Ionic LiquidsSanchez Merlinsky, LucianoHemmeter, DanielBaraldo Victorica, Luis MarioMaier, FlorianSteinruck, Hans PeterWilliams, Federico JoséRu polypyridineionic liquidhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Controlling the local concentration of metal complexes at the surface of ionic liquids (ILs) is a highly sought-after objective due to its pivotal implications in supported ionic liquid phase (SILP) catalysis. Equally important is to avoid per- and polyfluorinated substances due to environmental concerns. Herein, we investigate the surface enrichment of Ru polypyridyl complexes with fluorine-free alkylic side groups of varying lengths and shapes, using the hydrophilic IL [C2C1Im][OAc] as solvent. Additional charged carboxylate groups are included into the polypyridyl ligands to increase the solubility of the complex in the IL. When the ligand system is functionalized with long and hydrophobic alkyl side chains, the complex predominantly localizes at the IL/vacuum interface, as deduced from angle-resolved X-ray photoelectron spectroscopy. Conversely, in the presence of short or more bulky substituents, no surface enrichment is observed. This buoy-like behaviour with fluorine-free side groups is explored for 0.05 %mol to 1 %mol solutions. Intriguingly, surface saturation occurs at approximately 0.5 %mol, which is beneficial to the efficient operation of catalytic systems featuring high surface areas, such as SILP catalysts.Fil: Sanchez Merlinsky, Luciano. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Hemmeter, Daniel. Universitat Erlangen Nuremberg; AlemaniaFil: Baraldo Victorica, Luis Mario. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Maier, Florian. Universitat Erlangen Nuremberg; AlemaniaFil: Steinruck, Hans Peter. Universitat Erlangen Nuremberg; AlemaniaFil: Williams, Federico José. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaWiley2024-04info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/262187Sanchez Merlinsky, Luciano; Hemmeter, Daniel; Baraldo Victorica, Luis Mario; Maier, Florian; Steinruck, Hans Peter; et al.; Unlocking the Fluorine‐Free Buoy Effect: Surface‐Enriched Ruthenium Polypyridine Complexes in Ionic Liquids; Wiley; ChemistryOpen; 13; 7; 4-2024; 1-72191-1363CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/open.202400092info:eu-repo/semantics/altIdentifier/doi/10.1002/open.202400092info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:48:00Zoai:ri.conicet.gov.ar:11336/262187instacron: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 09:48:00.961CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Unlocking the Fluorine‐Free Buoy Effect: Surface‐Enriched Ruthenium Polypyridine Complexes in Ionic Liquids
title Unlocking the Fluorine‐Free Buoy Effect: Surface‐Enriched Ruthenium Polypyridine Complexes in Ionic Liquids
spellingShingle Unlocking the Fluorine‐Free Buoy Effect: Surface‐Enriched Ruthenium Polypyridine Complexes in Ionic Liquids
Sanchez Merlinsky, Luciano
Ru polypyridine
ionic liquid
title_short Unlocking the Fluorine‐Free Buoy Effect: Surface‐Enriched Ruthenium Polypyridine Complexes in Ionic Liquids
title_full Unlocking the Fluorine‐Free Buoy Effect: Surface‐Enriched Ruthenium Polypyridine Complexes in Ionic Liquids
title_fullStr Unlocking the Fluorine‐Free Buoy Effect: Surface‐Enriched Ruthenium Polypyridine Complexes in Ionic Liquids
title_full_unstemmed Unlocking the Fluorine‐Free Buoy Effect: Surface‐Enriched Ruthenium Polypyridine Complexes in Ionic Liquids
title_sort Unlocking the Fluorine‐Free Buoy Effect: Surface‐Enriched Ruthenium Polypyridine Complexes in Ionic Liquids
dc.creator.none.fl_str_mv Sanchez Merlinsky, Luciano
Hemmeter, Daniel
Baraldo Victorica, Luis Mario
Maier, Florian
Steinruck, Hans Peter
Williams, Federico José
author Sanchez Merlinsky, Luciano
author_facet Sanchez Merlinsky, Luciano
Hemmeter, Daniel
Baraldo Victorica, Luis Mario
Maier, Florian
Steinruck, Hans Peter
Williams, Federico José
author_role author
author2 Hemmeter, Daniel
Baraldo Victorica, Luis Mario
Maier, Florian
Steinruck, Hans Peter
Williams, Federico José
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv Ru polypyridine
ionic liquid
topic Ru polypyridine
ionic liquid
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Controlling the local concentration of metal complexes at the surface of ionic liquids (ILs) is a highly sought-after objective due to its pivotal implications in supported ionic liquid phase (SILP) catalysis. Equally important is to avoid per- and polyfluorinated substances due to environmental concerns. Herein, we investigate the surface enrichment of Ru polypyridyl complexes with fluorine-free alkylic side groups of varying lengths and shapes, using the hydrophilic IL [C2C1Im][OAc] as solvent. Additional charged carboxylate groups are included into the polypyridyl ligands to increase the solubility of the complex in the IL. When the ligand system is functionalized with long and hydrophobic alkyl side chains, the complex predominantly localizes at the IL/vacuum interface, as deduced from angle-resolved X-ray photoelectron spectroscopy. Conversely, in the presence of short or more bulky substituents, no surface enrichment is observed. This buoy-like behaviour with fluorine-free side groups is explored for 0.05 %mol to 1 %mol solutions. Intriguingly, surface saturation occurs at approximately 0.5 %mol, which is beneficial to the efficient operation of catalytic systems featuring high surface areas, such as SILP catalysts.
Fil: Sanchez Merlinsky, Luciano. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Hemmeter, Daniel. Universitat Erlangen Nuremberg; Alemania
Fil: Baraldo Victorica, Luis Mario. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Maier, Florian. Universitat Erlangen Nuremberg; Alemania
Fil: Steinruck, Hans Peter. Universitat Erlangen Nuremberg; Alemania
Fil: Williams, Federico José. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
description Controlling the local concentration of metal complexes at the surface of ionic liquids (ILs) is a highly sought-after objective due to its pivotal implications in supported ionic liquid phase (SILP) catalysis. Equally important is to avoid per- and polyfluorinated substances due to environmental concerns. Herein, we investigate the surface enrichment of Ru polypyridyl complexes with fluorine-free alkylic side groups of varying lengths and shapes, using the hydrophilic IL [C2C1Im][OAc] as solvent. Additional charged carboxylate groups are included into the polypyridyl ligands to increase the solubility of the complex in the IL. When the ligand system is functionalized with long and hydrophobic alkyl side chains, the complex predominantly localizes at the IL/vacuum interface, as deduced from angle-resolved X-ray photoelectron spectroscopy. Conversely, in the presence of short or more bulky substituents, no surface enrichment is observed. This buoy-like behaviour with fluorine-free side groups is explored for 0.05 %mol to 1 %mol solutions. Intriguingly, surface saturation occurs at approximately 0.5 %mol, which is beneficial to the efficient operation of catalytic systems featuring high surface areas, such as SILP catalysts.
publishDate 2024
dc.date.none.fl_str_mv 2024-04
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/11336/262187
Sanchez Merlinsky, Luciano; Hemmeter, Daniel; Baraldo Victorica, Luis Mario; Maier, Florian; Steinruck, Hans Peter; et al.; Unlocking the Fluorine‐Free Buoy Effect: Surface‐Enriched Ruthenium Polypyridine Complexes in Ionic Liquids; Wiley; ChemistryOpen; 13; 7; 4-2024; 1-7
2191-1363
CONICET Digital
CONICET
url http://hdl.handle.net/11336/262187
identifier_str_mv Sanchez Merlinsky, Luciano; Hemmeter, Daniel; Baraldo Victorica, Luis Mario; Maier, Florian; Steinruck, Hans Peter; et al.; Unlocking the Fluorine‐Free Buoy Effect: Surface‐Enriched Ruthenium Polypyridine Complexes in Ionic Liquids; Wiley; ChemistryOpen; 13; 7; 4-2024; 1-7
2191-1363
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://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/open.202400092
info:eu-repo/semantics/altIdentifier/doi/10.1002/open.202400092
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Wiley
publisher.none.fl_str_mv Wiley
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 13.13397

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