Electronic structure of the water oxidation catalyst cis, cis -[(bpy) 2(H 2O)Ru IIIORu III(OH 2)(bpy) 2] 4+, the blue dimer

Autores
Jurss, Jonah W.; Concepcion, Javier J.; Butler, Jennifer M.; Omberg, Kristin M.; Baraldo Victorica, Luis Mario; Thompson, Darla Graff; Lebeau, Estelle L.; Hornstein, Brooks; Schoonover, Jon R.; Jude, Hershel; Thompson, Joe D.; Dattelbaum, Dana M.; Rocha, Reginaldo C.; Templeton, Joseph L.; Meyer, Thomas J.
Año de publicación
2012
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The first designed molecular catalyst for water oxidation is the "blue dimer", cis,cis-[(bpy) 2(H 2O)Ru IIIORu III(OH 2)(bpy) 2] 4+. Although there is experimental evidence for extensive electronic coupling across the μ-oxo bridge, results of earlier DFT and CASSCF calculations provide a model with magnetic interactions of weak to moderately coupled Ru III ions across the μ-oxo bridge. We present the results of a comprehensive experimental investigation, combined with DFT calculations. The experiments demonstrate both that there is strong electronic coupling in the blue dimer and that its effects are profound. Experimental evidence has been obtained from molecular structures and key bond distances by XRD, electrochemically measured comproportionation constants for mixed-valence equilibria, temperature-dependent magnetism, chemical properties (solvent exchange, redox potentials, and pK a values), XPS binding energies, analysis of excitation-dependent resonance Raman profiles, and DFT analysis of electronic absorption spectra. The spectrum can be assigned based on a singlet ground state with specific hydrogen-bonding interactions with solvent molecules included. The results are in good agreement with available experimental data. The DFT analysis provides assignments for characteristic absorption bands in the near-IR and visible regions. Bridge-based dπ → dπ* and interconfiguration transitions at Ru III appear in the near-IR and MLCT and LMCT transitions in the visible. Reasonable values are also provided by DFT analysis for experimentally observed bond distances and redox potentials. The observed temperature-dependent magnetism of the blue dimer is consistent with a delocalized, diamagnetic singlet state (dπ 1*) 2 with a low-lying, paramagnetic triplet state (dπ 1*) 1(dπ 2*) 1. Systematic structural-magnetic-IR correlations are observed between ν sym(RuORu) and ν asym(RuORu) vibrational energies and magnetic properties in a series of ruthenium-based, μ-oxo-bridged complexes. Consistent with the DFT electronic structure model, bending along the Ru-O-Ru axis arises from a Jahn-Teller distortion with Ru-O-Ru dictated by the distortion and electron-electron repulsion. © 2012 American Chemical Society.
Fil: Jurss, Jonah W.. University of North Carolina; Estados Unidos
Fil: Concepcion, Javier J.. University of North Carolina; Estados Unidos
Fil: Butler, Jennifer M.. Los Alamos National Laboratory; Estados Unidos
Fil: Omberg, Kristin M.. Los Alamos National Laboratory; Estados Unidos
Fil: Baraldo Victorica, Luis Mario. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Los Alamos National Laboratory; Estados Unidos
Fil: Thompson, Darla Graff. Los Alamos National Laboratory; Estados Unidos
Fil: Lebeau, Estelle L.. Los Alamos National Laboratory; Estados Unidos
Fil: Hornstein, Brooks. Los Alamos National Laboratory; Estados Unidos
Fil: Schoonover, Jon R.. Los Alamos National Laboratory; Estados Unidos
Fil: Jude, Hershel. Los Alamos National Laboratory; Estados Unidos
Fil: Thompson, Joe D.. Los Alamos National Laboratory; Estados Unidos
Fil: Dattelbaum, Dana M.. Los Alamos National Laboratory; Estados Unidos
Fil: Rocha, Reginaldo C.. Los Alamos National Laboratory; Estados Unidos
Fil: Templeton, Joseph L.. University of North Carolina; Estados Unidos
Fil: Meyer, Thomas J.. University of North Carolina; Estados Unidos
Materia
Catalysis
Reaction Kinetics
Inorganic Reaction Mechanisms
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:11336/69484

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oai_identifier_str oai:ri.conicet.gov.ar:11336/69484
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repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Electronic structure of the water oxidation catalyst cis, cis -[(bpy) 2(H 2O)Ru IIIORu III(OH 2)(bpy) 2] 4+, the blue dimerJurss, Jonah W.Concepcion, Javier J.Butler, Jennifer M.Omberg, Kristin M.Baraldo Victorica, Luis MarioThompson, Darla GraffLebeau, Estelle L.Hornstein, BrooksSchoonover, Jon R.Jude, HershelThompson, Joe D.Dattelbaum, Dana M.Rocha, Reginaldo C.Templeton, Joseph L.Meyer, Thomas J.CatalysisReaction KineticsInorganic Reaction Mechanismshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The first designed molecular catalyst for water oxidation is the "blue dimer", cis,cis-[(bpy) 2(H 2O)Ru IIIORu III(OH 2)(bpy) 2] 4+. Although there is experimental evidence for extensive electronic coupling across the μ-oxo bridge, results of earlier DFT and CASSCF calculations provide a model with magnetic interactions of weak to moderately coupled Ru III ions across the μ-oxo bridge. We present the results of a comprehensive experimental investigation, combined with DFT calculations. The experiments demonstrate both that there is strong electronic coupling in the blue dimer and that its effects are profound. Experimental evidence has been obtained from molecular structures and key bond distances by XRD, electrochemically measured comproportionation constants for mixed-valence equilibria, temperature-dependent magnetism, chemical properties (solvent exchange, redox potentials, and pK a values), XPS binding energies, analysis of excitation-dependent resonance Raman profiles, and DFT analysis of electronic absorption spectra. The spectrum can be assigned based on a singlet ground state with specific hydrogen-bonding interactions with solvent molecules included. The results are in good agreement with available experimental data. The DFT analysis provides assignments for characteristic absorption bands in the near-IR and visible regions. Bridge-based dπ → dπ* and interconfiguration transitions at Ru III appear in the near-IR and MLCT and LMCT transitions in the visible. Reasonable values are also provided by DFT analysis for experimentally observed bond distances and redox potentials. The observed temperature-dependent magnetism of the blue dimer is consistent with a delocalized, diamagnetic singlet state (dπ 1*) 2 with a low-lying, paramagnetic triplet state (dπ 1*) 1(dπ 2*) 1. Systematic structural-magnetic-IR correlations are observed between ν sym(RuORu) and ν asym(RuORu) vibrational energies and magnetic properties in a series of ruthenium-based, μ-oxo-bridged complexes. Consistent with the DFT electronic structure model, bending along the Ru-O-Ru axis arises from a Jahn-Teller distortion with Ru-O-Ru dictated by the distortion and electron-electron repulsion. © 2012 American Chemical Society.Fil: Jurss, Jonah W.. University of North Carolina; Estados UnidosFil: Concepcion, Javier J.. University of North Carolina; Estados UnidosFil: Butler, Jennifer M.. Los Alamos National Laboratory; Estados UnidosFil: Omberg, Kristin M.. Los Alamos National Laboratory; Estados UnidosFil: Baraldo Victorica, Luis Mario. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Los Alamos National Laboratory; Estados UnidosFil: Thompson, Darla Graff. Los Alamos National Laboratory; Estados UnidosFil: Lebeau, Estelle L.. Los Alamos National Laboratory; Estados UnidosFil: Hornstein, Brooks. Los Alamos National Laboratory; Estados UnidosFil: Schoonover, Jon R.. Los Alamos National Laboratory; Estados UnidosFil: Jude, Hershel. Los Alamos National Laboratory; Estados UnidosFil: Thompson, Joe D.. Los Alamos National Laboratory; Estados UnidosFil: Dattelbaum, Dana M.. Los Alamos National Laboratory; Estados UnidosFil: Rocha, Reginaldo C.. Los Alamos National Laboratory; Estados UnidosFil: Templeton, Joseph L.. University of North Carolina; Estados UnidosFil: Meyer, Thomas J.. University of North Carolina; Estados UnidosAmerican Chemical Society2012-02info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/69484Jurss, Jonah W.; Concepcion, Javier J.; Butler, Jennifer M.; Omberg, Kristin M.; Baraldo Victorica, Luis Mario; et al.; Electronic structure of the water oxidation catalyst cis, cis -[(bpy) 2(H 2O)Ru IIIORu III(OH 2)(bpy) 2] 4+, the blue dimer; American Chemical Society; Inorganic Chemistry; 51; 3; 2-2012; 1345-13580020-1669CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/ic201521winfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/ic201521winfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:44:46Zoai:ri.conicet.gov.ar:11336/69484instacron: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 09:44:46.704CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Electronic structure of the water oxidation catalyst cis, cis -[(bpy) 2(H 2O)Ru IIIORu III(OH 2)(bpy) 2] 4+, the blue dimer
title Electronic structure of the water oxidation catalyst cis, cis -[(bpy) 2(H 2O)Ru IIIORu III(OH 2)(bpy) 2] 4+, the blue dimer
spellingShingle Electronic structure of the water oxidation catalyst cis, cis -[(bpy) 2(H 2O)Ru IIIORu III(OH 2)(bpy) 2] 4+, the blue dimer
Jurss, Jonah W.
Catalysis
Reaction Kinetics
Inorganic Reaction Mechanisms
title_short Electronic structure of the water oxidation catalyst cis, cis -[(bpy) 2(H 2O)Ru IIIORu III(OH 2)(bpy) 2] 4+, the blue dimer
title_full Electronic structure of the water oxidation catalyst cis, cis -[(bpy) 2(H 2O)Ru IIIORu III(OH 2)(bpy) 2] 4+, the blue dimer
title_fullStr Electronic structure of the water oxidation catalyst cis, cis -[(bpy) 2(H 2O)Ru IIIORu III(OH 2)(bpy) 2] 4+, the blue dimer
title_full_unstemmed Electronic structure of the water oxidation catalyst cis, cis -[(bpy) 2(H 2O)Ru IIIORu III(OH 2)(bpy) 2] 4+, the blue dimer
title_sort Electronic structure of the water oxidation catalyst cis, cis -[(bpy) 2(H 2O)Ru IIIORu III(OH 2)(bpy) 2] 4+, the blue dimer
dc.creator.none.fl_str_mv Jurss, Jonah W.
Concepcion, Javier J.
Butler, Jennifer M.
Omberg, Kristin M.
Baraldo Victorica, Luis Mario
Thompson, Darla Graff
Lebeau, Estelle L.
Hornstein, Brooks
Schoonover, Jon R.
Jude, Hershel
Thompson, Joe D.
Dattelbaum, Dana M.
Rocha, Reginaldo C.
Templeton, Joseph L.
Meyer, Thomas J.
author Jurss, Jonah W.
author_facet Jurss, Jonah W.
Concepcion, Javier J.
Butler, Jennifer M.
Omberg, Kristin M.
Baraldo Victorica, Luis Mario
Thompson, Darla Graff
Lebeau, Estelle L.
Hornstein, Brooks
Schoonover, Jon R.
Jude, Hershel
Thompson, Joe D.
Dattelbaum, Dana M.
Rocha, Reginaldo C.
Templeton, Joseph L.
Meyer, Thomas J.
author_role author
author2 Concepcion, Javier J.
Butler, Jennifer M.
Omberg, Kristin M.
Baraldo Victorica, Luis Mario
Thompson, Darla Graff
Lebeau, Estelle L.
Hornstein, Brooks
Schoonover, Jon R.
Jude, Hershel
Thompson, Joe D.
Dattelbaum, Dana M.
Rocha, Reginaldo C.
Templeton, Joseph L.
Meyer, Thomas J.
author2_role author
author
author
author
author
author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Catalysis
Reaction Kinetics
Inorganic Reaction Mechanisms
topic Catalysis
Reaction Kinetics
Inorganic Reaction Mechanisms
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 first designed molecular catalyst for water oxidation is the "blue dimer", cis,cis-[(bpy) 2(H 2O)Ru IIIORu III(OH 2)(bpy) 2] 4+. Although there is experimental evidence for extensive electronic coupling across the μ-oxo bridge, results of earlier DFT and CASSCF calculations provide a model with magnetic interactions of weak to moderately coupled Ru III ions across the μ-oxo bridge. We present the results of a comprehensive experimental investigation, combined with DFT calculations. The experiments demonstrate both that there is strong electronic coupling in the blue dimer and that its effects are profound. Experimental evidence has been obtained from molecular structures and key bond distances by XRD, electrochemically measured comproportionation constants for mixed-valence equilibria, temperature-dependent magnetism, chemical properties (solvent exchange, redox potentials, and pK a values), XPS binding energies, analysis of excitation-dependent resonance Raman profiles, and DFT analysis of electronic absorption spectra. The spectrum can be assigned based on a singlet ground state with specific hydrogen-bonding interactions with solvent molecules included. The results are in good agreement with available experimental data. The DFT analysis provides assignments for characteristic absorption bands in the near-IR and visible regions. Bridge-based dπ → dπ* and interconfiguration transitions at Ru III appear in the near-IR and MLCT and LMCT transitions in the visible. Reasonable values are also provided by DFT analysis for experimentally observed bond distances and redox potentials. The observed temperature-dependent magnetism of the blue dimer is consistent with a delocalized, diamagnetic singlet state (dπ 1*) 2 with a low-lying, paramagnetic triplet state (dπ 1*) 1(dπ 2*) 1. Systematic structural-magnetic-IR correlations are observed between ν sym(RuORu) and ν asym(RuORu) vibrational energies and magnetic properties in a series of ruthenium-based, μ-oxo-bridged complexes. Consistent with the DFT electronic structure model, bending along the Ru-O-Ru axis arises from a Jahn-Teller distortion with Ru-O-Ru dictated by the distortion and electron-electron repulsion. © 2012 American Chemical Society.
Fil: Jurss, Jonah W.. University of North Carolina; Estados Unidos
Fil: Concepcion, Javier J.. University of North Carolina; Estados Unidos
Fil: Butler, Jennifer M.. Los Alamos National Laboratory; Estados Unidos
Fil: Omberg, Kristin M.. Los Alamos National Laboratory; Estados Unidos
Fil: Baraldo Victorica, Luis Mario. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Los Alamos National Laboratory; Estados Unidos
Fil: Thompson, Darla Graff. Los Alamos National Laboratory; Estados Unidos
Fil: Lebeau, Estelle L.. Los Alamos National Laboratory; Estados Unidos
Fil: Hornstein, Brooks. Los Alamos National Laboratory; Estados Unidos
Fil: Schoonover, Jon R.. Los Alamos National Laboratory; Estados Unidos
Fil: Jude, Hershel. Los Alamos National Laboratory; Estados Unidos
Fil: Thompson, Joe D.. Los Alamos National Laboratory; Estados Unidos
Fil: Dattelbaum, Dana M.. Los Alamos National Laboratory; Estados Unidos
Fil: Rocha, Reginaldo C.. Los Alamos National Laboratory; Estados Unidos
Fil: Templeton, Joseph L.. University of North Carolina; Estados Unidos
Fil: Meyer, Thomas J.. University of North Carolina; Estados Unidos
description The first designed molecular catalyst for water oxidation is the "blue dimer", cis,cis-[(bpy) 2(H 2O)Ru IIIORu III(OH 2)(bpy) 2] 4+. Although there is experimental evidence for extensive electronic coupling across the μ-oxo bridge, results of earlier DFT and CASSCF calculations provide a model with magnetic interactions of weak to moderately coupled Ru III ions across the μ-oxo bridge. We present the results of a comprehensive experimental investigation, combined with DFT calculations. The experiments demonstrate both that there is strong electronic coupling in the blue dimer and that its effects are profound. Experimental evidence has been obtained from molecular structures and key bond distances by XRD, electrochemically measured comproportionation constants for mixed-valence equilibria, temperature-dependent magnetism, chemical properties (solvent exchange, redox potentials, and pK a values), XPS binding energies, analysis of excitation-dependent resonance Raman profiles, and DFT analysis of electronic absorption spectra. The spectrum can be assigned based on a singlet ground state with specific hydrogen-bonding interactions with solvent molecules included. The results are in good agreement with available experimental data. The DFT analysis provides assignments for characteristic absorption bands in the near-IR and visible regions. Bridge-based dπ → dπ* and interconfiguration transitions at Ru III appear in the near-IR and MLCT and LMCT transitions in the visible. Reasonable values are also provided by DFT analysis for experimentally observed bond distances and redox potentials. The observed temperature-dependent magnetism of the blue dimer is consistent with a delocalized, diamagnetic singlet state (dπ 1*) 2 with a low-lying, paramagnetic triplet state (dπ 1*) 1(dπ 2*) 1. Systematic structural-magnetic-IR correlations are observed between ν sym(RuORu) and ν asym(RuORu) vibrational energies and magnetic properties in a series of ruthenium-based, μ-oxo-bridged complexes. Consistent with the DFT electronic structure model, bending along the Ru-O-Ru axis arises from a Jahn-Teller distortion with Ru-O-Ru dictated by the distortion and electron-electron repulsion. © 2012 American Chemical Society.
publishDate 2012
dc.date.none.fl_str_mv 2012-02
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/11336/69484
Jurss, Jonah W.; Concepcion, Javier J.; Butler, Jennifer M.; Omberg, Kristin M.; Baraldo Victorica, Luis Mario; et al.; Electronic structure of the water oxidation catalyst cis, cis -[(bpy) 2(H 2O)Ru IIIORu III(OH 2)(bpy) 2] 4+, the blue dimer; American Chemical Society; Inorganic Chemistry; 51; 3; 2-2012; 1345-1358
0020-1669
CONICET Digital
CONICET
url http://hdl.handle.net/11336/69484
identifier_str_mv Jurss, Jonah W.; Concepcion, Javier J.; Butler, Jennifer M.; Omberg, Kristin M.; Baraldo Victorica, Luis Mario; et al.; Electronic structure of the water oxidation catalyst cis, cis -[(bpy) 2(H 2O)Ru IIIORu III(OH 2)(bpy) 2] 4+, the blue dimer; American Chemical Society; Inorganic Chemistry; 51; 3; 2-2012; 1345-1358
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/doi/10.1021/ic201521w
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/ic201521w
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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