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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/137012
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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) 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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1844613105476173824 |
score |
13.070432 |