Journal
INORGANIC CHEMISTRY
Volume 51, Issue 1, Pages 320-327Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic201668r
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Funding
- SOLAR-H2 [EU 212508]
- MICINN [CTQ2010-21497, CSD2006-0003]
- U.S. National Science Foundation [CHE09-52054]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [0952054] Funding Source: National Science Foundation
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A series of RuN6 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 NO2. 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).
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