One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O2/HO−

Autores
Maiti, Biplab K.; Maia, Luisa B.; Pal, Kuntal; Pakhira, Bholanath; Avilés,Teresa; Moura, Isabel; Pauleta, Sofia R.; Nuñez, José L.; Rizzi, Alberto Claudio; Brondino, Carlos Dante; Sarkar, Sabyasachi; Moura, José J. G.
Año de publicación
2014
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The complex [Ph4P]2[Cu(bdt)2] (1red) was synthesized by the reaction of [Ph4P]2[S2MoS2CuCl] with H2bdt (bdt = benzene-1,2-dithiolate) in basic medium. 1red is highly susceptible toward dioxygen, affording the one electron oxidized diamagnetic compound [Ph4P][Cu(bdt)2] (1ox). The interconversion between these two oxidation states can be switched by addition of O2 or base (Et4NOH = tetraethylammonium hydroxide), as demonstrated by cyclic voltammetry and UV–visible and EPR spectroscopies. Thiomolybdates, in free or complex forms with copper ions, play an important role in the stability of 1red during its synthesis, since in its absence, 1ox is isolated. Both 1red and 1ox were structurally characterized by X-ray crystallography. EPR experiments showed that 1red is a Cu(II)–sulfur complex and revealed strong covalency on the copper–sulfur bonds. DFT calculations confirmed the spin density delocalization over the four sulfur atoms (76%) and copper (24%) atom, suggesting that 1red has a “thiyl radical character”. Time dependent DFT calculations identified such ligand to ligand charge transfer transitions. Accordingly, 1red is better described by the two isoelectronic structures [CuI(bdt2, 4S3–,*)]2– ↔ [CuII(bdt2, 4S4–)]2–. On thermodynamic grounds, oxidation of 1red (doublet state) leads to 1ox singlet state, [CuIII(bdt2, 4S4–)]1–.
Fil: Maiti, Biplab K.. Universidade Nova de Lisboa; Portugal
Fil: Maia, Luisa B.. Universidade Nova de Lisboa; Portugal
Fil: Pal, Kuntal. University of Manchester; Reino Unido
Fil: Pakhira, Bholanath. Indian Institute of Engineering Science and Technology; India
Fil: Avilés,Teresa. Universidade Nova de Lisboa; Portugal
Fil: Moura, Isabel. Universidade Nova de Lisboa; Portugal
Fil: Pauleta, Sofia R.. Universidade Nova de Lisboa; Portugal
Fil: Nuñez, José L.. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina
Fil: Rizzi, Alberto Claudio. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina
Fil: Brondino, Carlos Dante. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina
Fil: Sarkar, Sabyasachi. Indian Institute of Engineering Science and Technology; India
Fil: Moura, José J. G.. Universidade Nova de Lisboa; Portugal
Materia
Copper
Epr
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:11336/31553
Acceder
id CONICETDig_668b5ec4bf8d5945f634391cbe233e00
oai_identifier_str oai:ri.conicet.gov.ar:11336/31553
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O2/HO−Maiti, Biplab K.Maia, Luisa B.Pal, KuntalPakhira, BholanathAvilés,TeresaMoura, IsabelPauleta, Sofia R.Nuñez, José L.Rizzi, Alberto ClaudioBrondino, Carlos DanteSarkar, SabyasachiMoura, José J. G.CopperEprhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The complex [Ph4P]2[Cu(bdt)2] (1red) was synthesized by the reaction of [Ph4P]2[S2MoS2CuCl] with H2bdt (bdt = benzene-1,2-dithiolate) in basic medium. 1red is highly susceptible toward dioxygen, affording the one electron oxidized diamagnetic compound [Ph4P][Cu(bdt)2] (1ox). The interconversion between these two oxidation states can be switched by addition of O2 or base (Et4NOH = tetraethylammonium hydroxide), as demonstrated by cyclic voltammetry and UV–visible and EPR spectroscopies. Thiomolybdates, in free or complex forms with copper ions, play an important role in the stability of 1red during its synthesis, since in its absence, 1ox is isolated. Both 1red and 1ox were structurally characterized by X-ray crystallography. EPR experiments showed that 1red is a Cu(II)–sulfur complex and revealed strong covalency on the copper–sulfur bonds. DFT calculations confirmed the spin density delocalization over the four sulfur atoms (76%) and copper (24%) atom, suggesting that 1red has a “thiyl radical character”. Time dependent DFT calculations identified such ligand to ligand charge transfer transitions. Accordingly, 1red is better described by the two isoelectronic structures [CuI(bdt2, 4S3–,*)]2– ↔ [CuII(bdt2, 4S4–)]2–. On thermodynamic grounds, oxidation of 1red (doublet state) leads to 1ox singlet state, [CuIII(bdt2, 4S4–)]1–.Fil: Maiti, Biplab K.. Universidade Nova de Lisboa; PortugalFil: Maia, Luisa B.. Universidade Nova de Lisboa; PortugalFil: Pal, Kuntal. University of Manchester; Reino UnidoFil: Pakhira, Bholanath. Indian Institute of Engineering Science and Technology; IndiaFil: Avilés,Teresa. Universidade Nova de Lisboa; PortugalFil: Moura, Isabel. Universidade Nova de Lisboa; PortugalFil: Pauleta, Sofia R.. Universidade Nova de Lisboa; PortugalFil: Nuñez, José L.. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; ArgentinaFil: Rizzi, Alberto Claudio. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; ArgentinaFil: Brondino, Carlos Dante. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; ArgentinaFil: Sarkar, Sabyasachi. Indian Institute of Engineering Science and Technology; IndiaFil: Moura, José J. G.. Universidade Nova de Lisboa; PortugalAmerican Chemical Society2014-12info: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/11336/31553Maia, Luisa B.; Moura, José J. G.; Sarkar, Sabyasachi; Brondino, Carlos Dante; Nuñez, José L.; Pauleta, Sofia R.; et al.; One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O2/HO−; American Chemical Society; Inorganic Chemistry; 53; 24; 12-2014; 12799-128080020-1669CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/ic501742jinfo:eu-repo/semantics/altIdentifier/doi/10.1021/ic501742info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-10T13:08:08Zoai:ri.conicet.gov.ar:11336/31553instacron: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:34982025-09-10 13:08:08.409CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O2/HO−
title One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O2/HO−
spellingShingle One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O2/HO−
Maiti, Biplab K.
Copper
Epr
title_short One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O2/HO−
title_full One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O2/HO−
title_fullStr One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O2/HO−
title_full_unstemmed One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O2/HO−
title_sort One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O2/HO−
dc.creator.none.fl_str_mv Maiti, Biplab K.
Maia, Luisa B.
Pal, Kuntal
Pakhira, Bholanath
Avilés,Teresa
Moura, Isabel
Pauleta, Sofia R.
Nuñez, José L.
Rizzi, Alberto Claudio
Brondino, Carlos Dante
Sarkar, Sabyasachi
Moura, José J. G.
author Maiti, Biplab K.
author_facet Maiti, Biplab K.
Maia, Luisa B.
Pal, Kuntal
Pakhira, Bholanath
Avilés,Teresa
Moura, Isabel
Pauleta, Sofia R.
Nuñez, José L.
Rizzi, Alberto Claudio
Brondino, Carlos Dante
Sarkar, Sabyasachi
Moura, José J. G.
author_role author
author2 Maia, Luisa B.
Pal, Kuntal
Pakhira, Bholanath
Avilés,Teresa
Moura, Isabel
Pauleta, Sofia R.
Nuñez, José L.
Rizzi, Alberto Claudio
Brondino, Carlos Dante
Sarkar, Sabyasachi
Moura, José J. G.
author2_role author
author
author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Copper
Epr
topic Copper
Epr
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 complex [Ph4P]2[Cu(bdt)2] (1red) was synthesized by the reaction of [Ph4P]2[S2MoS2CuCl] with H2bdt (bdt = benzene-1,2-dithiolate) in basic medium. 1red is highly susceptible toward dioxygen, affording the one electron oxidized diamagnetic compound [Ph4P][Cu(bdt)2] (1ox). The interconversion between these two oxidation states can be switched by addition of O2 or base (Et4NOH = tetraethylammonium hydroxide), as demonstrated by cyclic voltammetry and UV–visible and EPR spectroscopies. Thiomolybdates, in free or complex forms with copper ions, play an important role in the stability of 1red during its synthesis, since in its absence, 1ox is isolated. Both 1red and 1ox were structurally characterized by X-ray crystallography. EPR experiments showed that 1red is a Cu(II)–sulfur complex and revealed strong covalency on the copper–sulfur bonds. DFT calculations confirmed the spin density delocalization over the four sulfur atoms (76%) and copper (24%) atom, suggesting that 1red has a “thiyl radical character”. Time dependent DFT calculations identified such ligand to ligand charge transfer transitions. Accordingly, 1red is better described by the two isoelectronic structures [CuI(bdt2, 4S3–,*)]2– ↔ [CuII(bdt2, 4S4–)]2–. On thermodynamic grounds, oxidation of 1red (doublet state) leads to 1ox singlet state, [CuIII(bdt2, 4S4–)]1–.
Fil: Maiti, Biplab K.. Universidade Nova de Lisboa; Portugal
Fil: Maia, Luisa B.. Universidade Nova de Lisboa; Portugal
Fil: Pal, Kuntal. University of Manchester; Reino Unido
Fil: Pakhira, Bholanath. Indian Institute of Engineering Science and Technology; India
Fil: Avilés,Teresa. Universidade Nova de Lisboa; Portugal
Fil: Moura, Isabel. Universidade Nova de Lisboa; Portugal
Fil: Pauleta, Sofia R.. Universidade Nova de Lisboa; Portugal
Fil: Nuñez, José L.. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina
Fil: Rizzi, Alberto Claudio. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina
Fil: Brondino, Carlos Dante. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina
Fil: Sarkar, Sabyasachi. Indian Institute of Engineering Science and Technology; India
Fil: Moura, José J. G.. Universidade Nova de Lisboa; Portugal
description The complex [Ph4P]2[Cu(bdt)2] (1red) was synthesized by the reaction of [Ph4P]2[S2MoS2CuCl] with H2bdt (bdt = benzene-1,2-dithiolate) in basic medium. 1red is highly susceptible toward dioxygen, affording the one electron oxidized diamagnetic compound [Ph4P][Cu(bdt)2] (1ox). The interconversion between these two oxidation states can be switched by addition of O2 or base (Et4NOH = tetraethylammonium hydroxide), as demonstrated by cyclic voltammetry and UV–visible and EPR spectroscopies. Thiomolybdates, in free or complex forms with copper ions, play an important role in the stability of 1red during its synthesis, since in its absence, 1ox is isolated. Both 1red and 1ox were structurally characterized by X-ray crystallography. EPR experiments showed that 1red is a Cu(II)–sulfur complex and revealed strong covalency on the copper–sulfur bonds. DFT calculations confirmed the spin density delocalization over the four sulfur atoms (76%) and copper (24%) atom, suggesting that 1red has a “thiyl radical character”. Time dependent DFT calculations identified such ligand to ligand charge transfer transitions. Accordingly, 1red is better described by the two isoelectronic structures [CuI(bdt2, 4S3–,*)]2– ↔ [CuII(bdt2, 4S4–)]2–. On thermodynamic grounds, oxidation of 1red (doublet state) leads to 1ox singlet state, [CuIII(bdt2, 4S4–)]1–.
publishDate 2014
dc.date.none.fl_str_mv 2014-12
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/11336/31553
Maia, Luisa B.; Moura, José J. G.; Sarkar, Sabyasachi; Brondino, Carlos Dante; Nuñez, José L.; Pauleta, Sofia R.; et al.; One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O2/HO−; American Chemical Society; Inorganic Chemistry; 53; 24; 12-2014; 12799-12808
0020-1669
CONICET Digital
CONICET
url http://hdl.handle.net/11336/31553
identifier_str_mv Maia, Luisa B.; Moura, José J. G.; Sarkar, Sabyasachi; Brondino, Carlos Dante; Nuñez, José L.; Pauleta, Sofia R.; et al.; One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O2/HO−; American Chemical Society; Inorganic Chemistry; 53; 24; 12-2014; 12799-12808
0020-1669
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/ic501742j
info:eu-repo/semantics/altIdentifier/doi/10.1021/ic501742
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
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
_version_ 1842980379181449216
score 12.993085

Publicaciones similares