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Electronic Structur...
Electronic Structure of Oxidized Complexes Derived from cis-Ru(II)(bpy)(2)(H(2)O)(2)](2+) and Its Photoisomerization Mechanism
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Planas, Nora (author)
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Vigara, Laura (author)
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- Cady, Clyde (author)
- Uppsala universitet,Institutionen för fotokemi och molekylärvetenskap
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Miro, Pere (author)
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- Huang, Ping (author)
- Uppsala universitet,Molekylär biomimetik
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- Hammarström, Leif (author)
- Uppsala universitet,Kemisk fysik
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- Styring, Stenbjorn (author)
- Uppsala universitet,Molekylär biomimetik
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Leidel, Nils (author)
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Dau, Holger (author)
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Haumann, Michael (author)
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Gagliardi, Laura (author)
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Cramer, Christopher J. (author)
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Llobet, Antoni (author)
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(creator_code:org_t)
- 2011-10-12
- 2011
- English.
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In: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 50:21, s. 11134-11142
- Related links:
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https://urn.kb.se/re...
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https://doi.org/10.1...
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Abstract
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- 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.
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- By the author/editor
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Planas, Nora
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Vigara, Laura
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Cady, Clyde
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Miro, Pere
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Huang, Ping
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Hammarström, Lei ...
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show more...
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Styring, Stenbjo ...
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Leidel, Nils
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Dau, Holger
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Haumann, Michael
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Gagliardi, Laura
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Cramer, Christop ...
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Llobet, Antoni
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show less...
- Articles in the publication
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Inorganic Chemis ...
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Uppsala University