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dc.contributor.author
Jurss, Jonah W.  
dc.contributor.author
Concepcion, Javier J.  
dc.contributor.author
Butler, Jennifer M.  
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Omberg, Kristin M.  
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Baraldo Victorica, Luis Mario  
dc.contributor.author
Thompson, Darla Graff  
dc.contributor.author
Lebeau, Estelle L.  
dc.contributor.author
Hornstein, Brooks  
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Schoonover, Jon R.  
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Jude, Hershel  
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Thompson, Joe D.  
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Dattelbaum, Dana M.  
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Rocha, Reginaldo C.  
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Templeton, Joseph L.  
dc.contributor.author
Meyer, Thomas J.  
dc.date.available
2019-02-05T21:12:20Z  
dc.date.issued
2012-02  
dc.identifier.citation
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  
dc.identifier.issn
0020-1669  
dc.identifier.uri
http://hdl.handle.net/11336/69484  
dc.description.abstract
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.  
dc.format
application/pdf  
dc.language.iso
eng  
dc.publisher
American Chemical Society  
dc.rights
info:eu-repo/semantics/openAccess  
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/  
dc.subject
Catalysis  
dc.subject
Reaction Kinetics  
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Inorganic Reaction Mechanisms  
dc.subject.classification
Otras Ciencias Químicas  
dc.subject.classification
Ciencias Químicas  
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CIENCIAS NATURALES Y EXACTAS  
dc.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  
dc.type
info:eu-repo/semantics/article  
dc.type
info:ar-repo/semantics/artículo  
dc.type
info:eu-repo/semantics/publishedVersion  
dc.date.updated
2019-01-09T14:22:10Z  
dc.journal.volume
51  
dc.journal.number
3  
dc.journal.pagination
1345-1358  
dc.journal.pais
Estados Unidos  
dc.journal.ciudad
Washington  
dc.description.fil
Fil: Jurss, Jonah W.. University of North Carolina; Estados Unidos  
dc.description.fil
Fil: Concepcion, Javier J.. University of North Carolina; Estados Unidos  
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Fil: Butler, Jennifer M.. Los Alamos National Laboratory; Estados Unidos  
dc.description.fil
Fil: Omberg, Kristin M.. Los Alamos National Laboratory; Estados Unidos  
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Fil: Baraldo Victorica, Luis Mario. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Los Alamos National Laboratory; Estados Unidos  
dc.description.fil
Fil: Thompson, Darla Graff. Los Alamos National Laboratory; Estados Unidos  
dc.description.fil
Fil: Lebeau, Estelle L.. Los Alamos National Laboratory; Estados Unidos  
dc.description.fil
Fil: Hornstein, Brooks. Los Alamos National Laboratory; Estados Unidos  
dc.description.fil
Fil: Schoonover, Jon R.. Los Alamos National Laboratory; Estados Unidos  
dc.description.fil
Fil: Jude, Hershel. Los Alamos National Laboratory; Estados Unidos  
dc.description.fil
Fil: Thompson, Joe D.. Los Alamos National Laboratory; Estados Unidos  
dc.description.fil
Fil: Dattelbaum, Dana M.. Los Alamos National Laboratory; Estados Unidos  
dc.description.fil
Fil: Rocha, Reginaldo C.. Los Alamos National Laboratory; Estados Unidos  
dc.description.fil
Fil: Templeton, Joseph L.. University of North Carolina; Estados Unidos  
dc.description.fil
Fil: Meyer, Thomas J.. University of North Carolina; Estados Unidos  
dc.journal.title
Inorganic Chemistry  
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/https://dx.doi.org/10.1021/ic201521w  
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/ic201521w