A new zwitterionic, water soluble, Re(I) complex: Synthesis, spectroscopic and computational characterization

Autores
Martínez Saavedra, Héctor Hernando; Franca, Carlos Alberto; Petroselli, Gabriela; Erra Balsells, Rosa; Ruiz, Gustavo Teodosio; Wolcan, Ezequiel
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
A new water soluble Re(I) complex with a zwitterionic structure, Bu4N[(bpy)Re(CO)3(dcbpy)] (where Bu ¼ butyl; bpy ¼ 4,40 -bipyridine; dcbpy ¼ 2,20 -bipyridine-5,50 -dicarboxylate), was successfully synthesized and characterized by elemental analysis, 1 H NMR, FTIR and ESI. Protonation studies in aqueous solutions of the Re(I) complex showed three acidebase equilibriums with pKa1 ¼ 5.0, pKa2 ¼ 3.0 and pKa3 ¼ 2.0. pKa1 was assigned to the protonation equilibrium at bpy while pKa2 and pKa3 could be ascribed to protonation/deprotonation of the two carboxylates groups in the dcbpy ligand. With the aid of TD-DFT calculations the nature of the electronic transitions responsible for the pH-dependent UVevis spectroscopy of the Re(I) complex was identified. At pH ¼ 7 the lower energy band of the complex has MLLCTRe(CO)3/dcbpy character while at pH < 2 it switches to MLLCTRe(CO)3/bpy. This change in the nature of the lower energy band is responsible for the overall spectral changes in the 350e500 nm range after protonation of the Re(I) complex.
Fil: Martínez Saavedra, Héctor Hernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Franca, Carlos Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Centro de Química Inorgánica; Argentina. Universidad Nacional de La Plata; Argentina
Fil: Petroselli, Gabriela. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono; Argentina
Fil: Erra Balsells, Rosa. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono; Argentina
Fil: Ruiz, Gustavo Teodosio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Wolcan, Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Materia
Re(I) Complex
Zwitterionic
Mllct
Acid-Base Equilibriums
Td-Dft
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/2113
Acceder
id CONICETDig_f7558892bb6b033b759a4da7b0022243
oai_identifier_str oai:ri.conicet.gov.ar:11336/2113
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling A new zwitterionic, water soluble, Re(I) complex: Synthesis, spectroscopic and computational characterizationMartínez Saavedra, Héctor HernandoFranca, Carlos AlbertoPetroselli, GabrielaErra Balsells, RosaRuiz, Gustavo TeodosioWolcan, EzequielRe(I) ComplexZwitterionicMllctAcid-Base EquilibriumsTd-Dfthttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1A new water soluble Re(I) complex with a zwitterionic structure, Bu4N[(bpy)Re(CO)3(dcbpy)] (where Bu ¼ butyl; bpy ¼ 4,40 -bipyridine; dcbpy ¼ 2,20 -bipyridine-5,50 -dicarboxylate), was successfully synthesized and characterized by elemental analysis, 1 H NMR, FTIR and ESI. Protonation studies in aqueous solutions of the Re(I) complex showed three acidebase equilibriums with pKa1 ¼ 5.0, pKa2 ¼ 3.0 and pKa3 ¼ 2.0. pKa1 was assigned to the protonation equilibrium at bpy while pKa2 and pKa3 could be ascribed to protonation/deprotonation of the two carboxylates groups in the dcbpy ligand. With the aid of TD-DFT calculations the nature of the electronic transitions responsible for the pH-dependent UVevis spectroscopy of the Re(I) complex was identified. At pH ¼ 7 the lower energy band of the complex has MLLCTRe(CO)3/dcbpy character while at pH < 2 it switches to MLLCTRe(CO)3/bpy. This change in the nature of the lower energy band is responsible for the overall spectral changes in the 350e500 nm range after protonation of the Re(I) complex.Fil: Martínez Saavedra, Héctor Hernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Franca, Carlos Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Centro de Química Inorgánica; Argentina. Universidad Nacional de La Plata; ArgentinaFil: Petroselli, Gabriela. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono; ArgentinaFil: Erra Balsells, Rosa. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono; ArgentinaFil: Ruiz, Gustavo Teodosio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Wolcan, Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaElsevier2013-11-15info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/2113Martínez Saavedra, Héctor Hernando; Franca, Carlos Alberto; Petroselli, Gabriela; Erra Balsells, Rosa; Ruiz, Gustavo Teodosio; et al.; A new zwitterionic, water soluble, Re(I) complex: Synthesis, spectroscopic and computational characterization; Elsevier; Journal of Organometallic Chemistry; 745-746; 15-11-2013; 470-4780022-328Xenginfo:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0022328X13006608info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jorganchem.2013.08.038info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:03:52Zoai:ri.conicet.gov.ar:11336/2113instacron: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 11:03:52.673CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv A new zwitterionic, water soluble, Re(I) complex: Synthesis, spectroscopic and computational characterization
title A new zwitterionic, water soluble, Re(I) complex: Synthesis, spectroscopic and computational characterization
spellingShingle A new zwitterionic, water soluble, Re(I) complex: Synthesis, spectroscopic and computational characterization
Martínez Saavedra, Héctor Hernando
Re(I) Complex
Zwitterionic
Mllct
Acid-Base Equilibriums
Td-Dft
title_short A new zwitterionic, water soluble, Re(I) complex: Synthesis, spectroscopic and computational characterization
title_full A new zwitterionic, water soluble, Re(I) complex: Synthesis, spectroscopic and computational characterization
title_fullStr A new zwitterionic, water soluble, Re(I) complex: Synthesis, spectroscopic and computational characterization
title_full_unstemmed A new zwitterionic, water soluble, Re(I) complex: Synthesis, spectroscopic and computational characterization
title_sort A new zwitterionic, water soluble, Re(I) complex: Synthesis, spectroscopic and computational characterization
dc.creator.none.fl_str_mv Martínez Saavedra, Héctor Hernando
Franca, Carlos Alberto
Petroselli, Gabriela
Erra Balsells, Rosa
Ruiz, Gustavo Teodosio
Wolcan, Ezequiel
author Martínez Saavedra, Héctor Hernando
author_facet Martínez Saavedra, Héctor Hernando
Franca, Carlos Alberto
Petroselli, Gabriela
Erra Balsells, Rosa
Ruiz, Gustavo Teodosio
Wolcan, Ezequiel
author_role author
author2 Franca, Carlos Alberto
Petroselli, Gabriela
Erra Balsells, Rosa
Ruiz, Gustavo Teodosio
Wolcan, Ezequiel
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv Re(I) Complex
Zwitterionic
Mllct
Acid-Base Equilibriums
Td-Dft
topic Re(I) Complex
Zwitterionic
Mllct
Acid-Base Equilibriums
Td-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 A new water soluble Re(I) complex with a zwitterionic structure, Bu4N[(bpy)Re(CO)3(dcbpy)] (where Bu ¼ butyl; bpy ¼ 4,40 -bipyridine; dcbpy ¼ 2,20 -bipyridine-5,50 -dicarboxylate), was successfully synthesized and characterized by elemental analysis, 1 H NMR, FTIR and ESI. Protonation studies in aqueous solutions of the Re(I) complex showed three acidebase equilibriums with pKa1 ¼ 5.0, pKa2 ¼ 3.0 and pKa3 ¼ 2.0. pKa1 was assigned to the protonation equilibrium at bpy while pKa2 and pKa3 could be ascribed to protonation/deprotonation of the two carboxylates groups in the dcbpy ligand. With the aid of TD-DFT calculations the nature of the electronic transitions responsible for the pH-dependent UVevis spectroscopy of the Re(I) complex was identified. At pH ¼ 7 the lower energy band of the complex has MLLCTRe(CO)3/dcbpy character while at pH < 2 it switches to MLLCTRe(CO)3/bpy. This change in the nature of the lower energy band is responsible for the overall spectral changes in the 350e500 nm range after protonation of the Re(I) complex.
Fil: Martínez Saavedra, Héctor Hernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Franca, Carlos Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Centro de Química Inorgánica; Argentina. Universidad Nacional de La Plata; Argentina
Fil: Petroselli, Gabriela. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono; Argentina
Fil: Erra Balsells, Rosa. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono; Argentina
Fil: Ruiz, Gustavo Teodosio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Wolcan, Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
description A new water soluble Re(I) complex with a zwitterionic structure, Bu4N[(bpy)Re(CO)3(dcbpy)] (where Bu ¼ butyl; bpy ¼ 4,40 -bipyridine; dcbpy ¼ 2,20 -bipyridine-5,50 -dicarboxylate), was successfully synthesized and characterized by elemental analysis, 1 H NMR, FTIR and ESI. Protonation studies in aqueous solutions of the Re(I) complex showed three acidebase equilibriums with pKa1 ¼ 5.0, pKa2 ¼ 3.0 and pKa3 ¼ 2.0. pKa1 was assigned to the protonation equilibrium at bpy while pKa2 and pKa3 could be ascribed to protonation/deprotonation of the two carboxylates groups in the dcbpy ligand. With the aid of TD-DFT calculations the nature of the electronic transitions responsible for the pH-dependent UVevis spectroscopy of the Re(I) complex was identified. At pH ¼ 7 the lower energy band of the complex has MLLCTRe(CO)3/dcbpy character while at pH < 2 it switches to MLLCTRe(CO)3/bpy. This change in the nature of the lower energy band is responsible for the overall spectral changes in the 350e500 nm range after protonation of the Re(I) complex.
publishDate 2013
dc.date.none.fl_str_mv 2013-11-15
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/11336/2113
Martínez Saavedra, Héctor Hernando; Franca, Carlos Alberto; Petroselli, Gabriela; Erra Balsells, Rosa; Ruiz, Gustavo Teodosio; et al.; A new zwitterionic, water soluble, Re(I) complex: Synthesis, spectroscopic and computational characterization; Elsevier; Journal of Organometallic Chemistry; 745-746; 15-11-2013; 470-478
0022-328X
url http://hdl.handle.net/11336/2113
identifier_str_mv Martínez Saavedra, Héctor Hernando; Franca, Carlos Alberto; Petroselli, Gabriela; Erra Balsells, Rosa; Ruiz, Gustavo Teodosio; et al.; A new zwitterionic, water soluble, Re(I) complex: Synthesis, spectroscopic and computational characterization; Elsevier; Journal of Organometallic Chemistry; 745-746; 15-11-2013; 470-478
0022-328X
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0022328X13006608
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jorganchem.2013.08.038
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
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
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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