Electrochemical and Photophysical Properties of Ruthenium(II) Complexes Equipped with Sulfurated Bipyridine Ligands

Autores
Hua, Shao-An; Cattaneo, Mauricio; Oelschlegel, Manuel; Heindl, Moritz; Schmid, Lucius; Dechert, Sebastian; Wenger, Oliver S.; Siewert, Inke; González, Leticia; Meyer, Franc
Año de publicación
2020
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The development of new solar-to-fuel scenarios is of great importance, but the construction of molecular systems that convert sunlight into chemical energy represents a challenge. One specific issue is that the molecular systems have to be able to accumulate redox equivalents to mediate the photodriven transformation of relevant small molecules, which mostly involves the orchestrated transfer of multiple electrons and protons. Disulfide/dithiol interconversions are prominent 2e-/2H+ couples and can play an important role for redox control and charge storage. With this background in mind, a new photosensitizer [Ru(S-Sbpy)(bpy)2]2+ (12+) equipped with a disulfide functionalized bpy ligand (S-Sbpy, bpy = 2,2′-bipyridine) was synthesized and has been comprehensively studied, including structural characterization by X-ray diffraction. In-depth electrochemical studies show that the S-Sbpy ligand in 12+ can be reduced twice at moderate potentials (around-1.1 V vs Fc+/0), and simulation of the cyclic voltammetry (CV) traces revealed potential inversion (E2 > E1) and allowed to derive kinetic parameters for the sequential electron-transfer processes. However, reduction at room temperature also triggers the ejection of one sulfur atom from 12+, leading to the formation of [Ru(Sbpy)(bpy)2]2+(22+). This chemical reaction can be suppressed by decreasing the temperature from 298 to 248 K. Compared to the archetypical photosensitizer [Ru(bpy)3]2+, 12+ features an additional low energy optical excitation in the MLCT region, originating from charge transfer from the metal center to the S-Sbpy ligand (aka MSCT) according to time-dependent density functional theory (TD-DFT) calculations. Analysis of the excited states of 12+ on the basis of ground-state Wigner sampling and using charge-transfer descriptors has shown that bpy modification with a peripheral disulfide moiety leads to an energy splitting between charge-transfer excitations to the S-Sbpy and the bpy ligands, offering the possibility of selective charge transfer from the metal to either type of ligands. Compound 12+ is photostable and shows an emission from a 3MLCT state in deoxygenated acetonitrile with a lifetime of 109 ns. This work demonstrates a rationally designed system that enables future studies of photoinduced multielectron, multiproton PCET chemistry.
Fil: Hua, Shao-An. Universität Göttingen; Alemania
Fil: Cattaneo, Mauricio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Oelschlegel, Manuel. Universität Göttingen; Alemania
Fil: Heindl, Moritz. Universidad de Viena; Austria
Fil: Schmid, Lucius. Universidad de Basilea; Suiza
Fil: Dechert, Sebastian. Universität Göttingen; Alemania
Fil: Wenger, Oliver S.. Universidad de Basilea; Suiza
Fil: Siewert, Inke. Universität Göttingen; Alemania
Fil: González, Leticia. Universidad de Viena; Austria
Fil: Meyer, Franc. Universität Göttingen; Alemania
Materia
ruthenium complexes
disulfide
electrochemistry
multiredox
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:11336/137012

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oai_identifier_str oai:ri.conicet.gov.ar:11336/137012
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repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Electrochemical and Photophysical Properties of Ruthenium(II) Complexes Equipped with Sulfurated Bipyridine LigandsHua, Shao-AnCattaneo, MauricioOelschlegel, ManuelHeindl, MoritzSchmid, LuciusDechert, SebastianWenger, Oliver S.Siewert, InkeGonzález, LeticiaMeyer, Francruthenium complexesdisulfideelectrochemistrymultiredoxhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The development of new solar-to-fuel scenarios is of great importance, but the construction of molecular systems that convert sunlight into chemical energy represents a challenge. One specific issue is that the molecular systems have to be able to accumulate redox equivalents to mediate the photodriven transformation of relevant small molecules, which mostly involves the orchestrated transfer of multiple electrons and protons. Disulfide/dithiol interconversions are prominent 2e-/2H+ couples and can play an important role for redox control and charge storage. With this background in mind, a new photosensitizer [Ru(S-Sbpy)(bpy)2]2+ (12+) equipped with a disulfide functionalized bpy ligand (S-Sbpy, bpy = 2,2′-bipyridine) was synthesized and has been comprehensively studied, including structural characterization by X-ray diffraction. In-depth electrochemical studies show that the S-Sbpy ligand in 12+ can be reduced twice at moderate potentials (around-1.1 V vs Fc+/0), and simulation of the cyclic voltammetry (CV) traces revealed potential inversion (E2 > E1) and allowed to derive kinetic parameters for the sequential electron-transfer processes. However, reduction at room temperature also triggers the ejection of one sulfur atom from 12+, leading to the formation of [Ru(Sbpy)(bpy)2]2+(22+). This chemical reaction can be suppressed by decreasing the temperature from 298 to 248 K. Compared to the archetypical photosensitizer [Ru(bpy)3]2+, 12+ features an additional low energy optical excitation in the MLCT region, originating from charge transfer from the metal center to the S-Sbpy ligand (aka MSCT) according to time-dependent density functional theory (TD-DFT) calculations. Analysis of the excited states of 12+ on the basis of ground-state Wigner sampling and using charge-transfer descriptors has shown that bpy modification with a peripheral disulfide moiety leads to an energy splitting between charge-transfer excitations to the S-Sbpy and the bpy ligands, offering the possibility of selective charge transfer from the metal to either type of ligands. Compound 12+ is photostable and shows an emission from a 3MLCT state in deoxygenated acetonitrile with a lifetime of 109 ns. This work demonstrates a rationally designed system that enables future studies of photoinduced multielectron, multiproton PCET chemistry.Fil: Hua, Shao-An. Universität Göttingen; AlemaniaFil: Cattaneo, Mauricio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; ArgentinaFil: Oelschlegel, Manuel. Universität Göttingen; AlemaniaFil: Heindl, Moritz. Universidad de Viena; AustriaFil: Schmid, Lucius. Universidad de Basilea; SuizaFil: Dechert, Sebastian. Universität Göttingen; AlemaniaFil: Wenger, Oliver S.. Universidad de Basilea; SuizaFil: Siewert, Inke. Universität Göttingen; AlemaniaFil: González, Leticia. Universidad de Viena; AustriaFil: Meyer, Franc. Universität Göttingen; AlemaniaAmerican Chemical Society2020-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/137012Hua, Shao-An; Cattaneo, Mauricio; Oelschlegel, Manuel; Heindl, Moritz; Schmid, Lucius; et al.; Electrochemical and Photophysical Properties of Ruthenium(II) Complexes Equipped with Sulfurated Bipyridine Ligands; American Chemical Society; Inorganic Chemistry; 59; 7; 3-2020; 4972-49840020-1669CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.0c00220info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.inorgchem.0c00220info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:35:29Zoai:ri.conicet.gov.ar:11336/137012instacron: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 09:35:29.911CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Electrochemical and Photophysical Properties of Ruthenium(II) Complexes Equipped with Sulfurated Bipyridine Ligands
title Electrochemical and Photophysical Properties of Ruthenium(II) Complexes Equipped with Sulfurated Bipyridine Ligands
spellingShingle Electrochemical and Photophysical Properties of Ruthenium(II) Complexes Equipped with Sulfurated Bipyridine Ligands
Hua, Shao-An
ruthenium complexes
disulfide
electrochemistry
multiredox
title_short Electrochemical and Photophysical Properties of Ruthenium(II) Complexes Equipped with Sulfurated Bipyridine Ligands
title_full Electrochemical and Photophysical Properties of Ruthenium(II) Complexes Equipped with Sulfurated Bipyridine Ligands
title_fullStr Electrochemical and Photophysical Properties of Ruthenium(II) Complexes Equipped with Sulfurated Bipyridine Ligands
title_full_unstemmed Electrochemical and Photophysical Properties of Ruthenium(II) Complexes Equipped with Sulfurated Bipyridine Ligands
title_sort Electrochemical and Photophysical Properties of Ruthenium(II) Complexes Equipped with Sulfurated Bipyridine Ligands
dc.creator.none.fl_str_mv Hua, Shao-An
Cattaneo, Mauricio
Oelschlegel, Manuel
Heindl, Moritz
Schmid, Lucius
Dechert, Sebastian
Wenger, Oliver S.
Siewert, Inke
González, Leticia
Meyer, Franc
author Hua, Shao-An
author_facet Hua, Shao-An
Cattaneo, Mauricio
Oelschlegel, Manuel
Heindl, Moritz
Schmid, Lucius
Dechert, Sebastian
Wenger, Oliver S.
Siewert, Inke
González, Leticia
Meyer, Franc
author_role author
author2 Cattaneo, Mauricio
Oelschlegel, Manuel
Heindl, Moritz
Schmid, Lucius
Dechert, Sebastian
Wenger, Oliver S.
Siewert, Inke
González, Leticia
Meyer, Franc
author2_role author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv ruthenium complexes
disulfide
electrochemistry
multiredox
topic ruthenium complexes
disulfide
electrochemistry
multiredox
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 development of new solar-to-fuel scenarios is of great importance, but the construction of molecular systems that convert sunlight into chemical energy represents a challenge. One specific issue is that the molecular systems have to be able to accumulate redox equivalents to mediate the photodriven transformation of relevant small molecules, which mostly involves the orchestrated transfer of multiple electrons and protons. Disulfide/dithiol interconversions are prominent 2e-/2H+ couples and can play an important role for redox control and charge storage. With this background in mind, a new photosensitizer [Ru(S-Sbpy)(bpy)2]2+ (12+) equipped with a disulfide functionalized bpy ligand (S-Sbpy, bpy = 2,2′-bipyridine) was synthesized and has been comprehensively studied, including structural characterization by X-ray diffraction. In-depth electrochemical studies show that the S-Sbpy ligand in 12+ can be reduced twice at moderate potentials (around-1.1 V vs Fc+/0), and simulation of the cyclic voltammetry (CV) traces revealed potential inversion (E2 > E1) and allowed to derive kinetic parameters for the sequential electron-transfer processes. However, reduction at room temperature also triggers the ejection of one sulfur atom from 12+, leading to the formation of [Ru(Sbpy)(bpy)2]2+(22+). This chemical reaction can be suppressed by decreasing the temperature from 298 to 248 K. Compared to the archetypical photosensitizer [Ru(bpy)3]2+, 12+ features an additional low energy optical excitation in the MLCT region, originating from charge transfer from the metal center to the S-Sbpy ligand (aka MSCT) according to time-dependent density functional theory (TD-DFT) calculations. Analysis of the excited states of 12+ on the basis of ground-state Wigner sampling and using charge-transfer descriptors has shown that bpy modification with a peripheral disulfide moiety leads to an energy splitting between charge-transfer excitations to the S-Sbpy and the bpy ligands, offering the possibility of selective charge transfer from the metal to either type of ligands. Compound 12+ is photostable and shows an emission from a 3MLCT state in deoxygenated acetonitrile with a lifetime of 109 ns. This work demonstrates a rationally designed system that enables future studies of photoinduced multielectron, multiproton PCET chemistry.
Fil: Hua, Shao-An. Universität Göttingen; Alemania
Fil: Cattaneo, Mauricio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Oelschlegel, Manuel. Universität Göttingen; Alemania
Fil: Heindl, Moritz. Universidad de Viena; Austria
Fil: Schmid, Lucius. Universidad de Basilea; Suiza
Fil: Dechert, Sebastian. Universität Göttingen; Alemania
Fil: Wenger, Oliver S.. Universidad de Basilea; Suiza
Fil: Siewert, Inke. Universität Göttingen; Alemania
Fil: González, Leticia. Universidad de Viena; Austria
Fil: Meyer, Franc. Universität Göttingen; Alemania
description The development of new solar-to-fuel scenarios is of great importance, but the construction of molecular systems that convert sunlight into chemical energy represents a challenge. One specific issue is that the molecular systems have to be able to accumulate redox equivalents to mediate the photodriven transformation of relevant small molecules, which mostly involves the orchestrated transfer of multiple electrons and protons. Disulfide/dithiol interconversions are prominent 2e-/2H+ couples and can play an important role for redox control and charge storage. With this background in mind, a new photosensitizer [Ru(S-Sbpy)(bpy)2]2+ (12+) equipped with a disulfide functionalized bpy ligand (S-Sbpy, bpy = 2,2′-bipyridine) was synthesized and has been comprehensively studied, including structural characterization by X-ray diffraction. In-depth electrochemical studies show that the S-Sbpy ligand in 12+ can be reduced twice at moderate potentials (around-1.1 V vs Fc+/0), and simulation of the cyclic voltammetry (CV) traces revealed potential inversion (E2 > E1) and allowed to derive kinetic parameters for the sequential electron-transfer processes. However, reduction at room temperature also triggers the ejection of one sulfur atom from 12+, leading to the formation of [Ru(Sbpy)(bpy)2]2+(22+). This chemical reaction can be suppressed by decreasing the temperature from 298 to 248 K. Compared to the archetypical photosensitizer [Ru(bpy)3]2+, 12+ features an additional low energy optical excitation in the MLCT region, originating from charge transfer from the metal center to the S-Sbpy ligand (aka MSCT) according to time-dependent density functional theory (TD-DFT) calculations. Analysis of the excited states of 12+ on the basis of ground-state Wigner sampling and using charge-transfer descriptors has shown that bpy modification with a peripheral disulfide moiety leads to an energy splitting between charge-transfer excitations to the S-Sbpy and the bpy ligands, offering the possibility of selective charge transfer from the metal to either type of ligands. Compound 12+ is photostable and shows an emission from a 3MLCT state in deoxygenated acetonitrile with a lifetime of 109 ns. This work demonstrates a rationally designed system that enables future studies of photoinduced multielectron, multiproton PCET chemistry.
publishDate 2020
dc.date.none.fl_str_mv 2020-03
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/11336/137012
Hua, Shao-An; Cattaneo, Mauricio; Oelschlegel, Manuel; Heindl, Moritz; Schmid, Lucius; et al.; Electrochemical and Photophysical Properties of Ruthenium(II) Complexes Equipped with Sulfurated Bipyridine Ligands; American Chemical Society; Inorganic Chemistry; 59; 7; 3-2020; 4972-4984
0020-1669
CONICET Digital
CONICET
url http://hdl.handle.net/11336/137012
identifier_str_mv Hua, Shao-An; Cattaneo, Mauricio; Oelschlegel, Manuel; Heindl, Moritz; Schmid, Lucius; et al.; Electrochemical and Photophysical Properties of Ruthenium(II) Complexes Equipped with Sulfurated Bipyridine Ligands; American Chemical Society; Inorganic Chemistry; 59; 7; 3-2020; 4972-4984
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/https://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.0c00220
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.inorgchem.0c00220
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
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)
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reponame_str CONICET Digital (CONICET)
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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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