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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/69484
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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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1844613408866959360 |
score |
13.070432 |