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Synthesis, Structure, and Electronic Properties of RuN(6) Dinuclear Ru-Hbpp Complexes
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
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2012 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 51, no 1, 320-327 p.Article in journal (Refereed) Published
Abstract [en]

A series of RuN(6) dinuclear Ru-Hbpp complexes (Hbpp is the dinucleating tetraaza ligand 3,5-bis(pyridyl)pyrazole) of general formula {[Ru(II)(R(2)-trpy)(MeCN)](2)(mu-R(1)-bpp)}3(+), 10(3+)-14(3+), (R(1) = H, Me, or NO(2). and R(2) = H, Me, MeO; see Scheme 1) has been prepared from their Cl(-) or AcO(-) bridged precursors. The complexes have been characterized by UV-vis, NMR, CV, and some by X-ray. Complexes 10(3+)-14(3+), Ru(2)(II,II), were oxidized by 1 equiv in solution, leading to the mixed valence Ru(2)(II,III) complexes 10(4+)-14(4+) containing one unpaired electron and were characterized by EPR and UV-vis-near-IR, which showed metal-centered spin and the presence of low-energy IVCT bands. The H(ab) parameter indicates a relatively strong electronic coupling between the two ruthenium centers (class II). Further two electron oxidation in solution of the 10(3+)-14(3+) led to the formation of EPR silent Ru(2)(II,III) complexes 10(5+)-14(5+), that were further characterized by UV-vis-NIR TD-DFT calculations are employed to assign the nature of the UV-vis transitions for the complexes in the various oxidation states, which are of metal to ligand charge transfer (MLCT) type for Ru(2)(II,II) and ligand to,m. metal charge transfer (LMCT) type for Ru(2)(III,II) and Ru(2)(III,III).

Place, publisher, year, edition, pages
2012. Vol. 51, no 1, 320-327 p.
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Chemical Sciences
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URN: urn:nbn:se:uu:diva-168594DOI: 10.1021/ic201668rISI: 000298712000044OAI: oai:DiVA.org:uu-168594DiVA: diva2:501522
Available from: 2012-02-14 Created: 2012-02-13 Last updated: 2017-12-07Bibliographically approved

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Lomoth, RainerHammarström, Leif

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