Journal article
Electronic Structure of Oxidized Complexes Derived from cis-Ru-II(bpy)(2)(H2O)(2)](2+) and Its Photoisomerization Mechanism
Inorganic chemistry, Vol.50(21), pp.11134-11142
11/07/2011
DOI: 10.1021/ic201686c
PMID: 21992177
Abstract
The geometry and electronic structure of cis-[Ru-II(bpy)(2)(H2O)(2)](2+) and its higher oxidation state species up formally to Ru-VI have been studied by means of UV-vis, EPR, XAS, and DFT and CASSCF/CASPT2 calculations. DFT calculations of the molecular structures of these species show that, as the oxidation state increases, the Ru-O bond distance decreases, indicating increased degrees of Ru-O multiple bonding. In addition, the O-Ru-O valence bond angle increases as the oxidation state increases. EPR spectroscopy and quantum chemical calculations indicate that low-spin configurations are favored for all oxidation states. Thus, cis-[Ru-IV(bpy)(2)(OH)(0)](2+) (d(4)) has a singlet ground state and is EPR-silent at low temperatures, while cis-[Ru-V(bpy)(2)(O)(OH)](2+) (d(3)) has a doublet ground state. XAS spectroscopy of higher oxidation state species and DFT calculations further illuminate the electronic structures of these complexes, particularly with respect to the covalent character of the O-Ru-O fragment. In addition, the photochemical isomerization of cis-[Ru-II(bpy)(2)(H2O)(2)](2+) to its trans-[Ru-II(bpy)(2)(H2O)(2)](2+) isomer has been fully characterized through quantum chemical calculations. The excited-state process is predicted to involve decoordination of one aqua ligand, which leads to a coordinatively unsaturated complex that undergoes structural rearrangement followed by recoordination of water to yield the trans isomer.
Details
- Title: Subtitle
- Electronic Structure of Oxidized Complexes Derived from cis-Ru-II(bpy)(2)(H2O)(2)](2+) and Its Photoisomerization Mechanism
- Creators
- Nora Planas - Institut Català d'Investigació QuímicaLaura Vigara - Institut Català d'Investigació QuímicaClyde Cady - Uppsala UniversityPere Miro - University of MinnesotaPing Huang - Uppsala UniversityLeif Hammarstrom - Uppsala UniversityStenbjorn Styring - Uppsala UniversityNils Leidel - Freie Universität BerlinHolger Dau - Freie Universität BerlinMichael Haumann - Freie Universität BerlinLaura Gagliardi - University of MinnesotaChristopher J. Cramer - University of MinnesotaAntoni Llobet - Institut Català d'Investigació Química
- Resource Type
- Journal article
- Publication Details
- Inorganic chemistry, Vol.50(21), pp.11134-11142
- Publisher
- Amer Chemical Soc
- DOI
- 10.1021/ic201686c
- PMID
- 21992177
- ISSN
- 0020-1669
- eISSN
- 1520-510X
- Number of pages
- 9
- Grant note
- Ha3265/3-1 / Deutsche Forschungsgemeinschaft; German Research Foundation (DFG) CTQ2010-21497; CSD2006-0003 / MICINN; Ministry of Science and Innovation, Spain (MICINN); Spanish Government CIRIT/2009 SGR 69 / Generalitat de Catalunya K&A Wallenberg Foundation; Knut & Alice Wallenberg Foundation 0952054 / Division Of Chemistry; Direct For Mathematical & Physical Scien; National Science Foundation (NSF); NSF - Directorate for Mathematical & Physical Sciences (MPS) CHE09-52054 / U.S. National Science Foundation; National Science Foundation (NSF) EU 212508 / SOLAR-H2 Swedish Energy Agenc
- Language
- English
- Date published
- 11/07/2011
- Academic Unit
- Chemistry
- Record Identifier
- 9984618523002771
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