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Electronic Structure of Oxidized Complexes Derived from cis-Ru(II)(bpy)(2)(H(2)O)(2)](2+) and Its Photoisomerization Mechanism
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Photochemistry and Molecular Science.
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2011 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 50, no 21, 11134-11142 p.Article in journal (Refereed) Published
Abstract [en]

The geometry and electronic structure of cis-[Ru(II)(bpy)(2)(H(2)O)(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)(H(2)O)(2)](2+) to its trans-[Ru(II)(bpy)(2)(H(2)O)(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.

Place, publisher, year, edition, pages
2011. Vol. 50, no 21, 11134-11142 p.
National Category
Natural Sciences
URN: urn:nbn:se:uu:diva-164563DOI: 10.1021/ic201686cISI: 000296303900082OAI: oai:DiVA.org:uu-164563DiVA: diva2:468597
Available from: 2011-12-21 Created: 2011-12-21 Last updated: 2011-12-21Bibliographically approved

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Huang, PingHammarström, LeifStyring, Stenbjorn
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