Journal
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
Volume -, Issue 4, Pages 589-596Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.201001039
Keywords
Ruthenium; Copper; Dinuclear complexes; Dye-sensitized solar cells; Supramolecular chemistry
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Funding
- Excitonic Solar Cell Consortium (EPSRC)
- EaStCHEM Research Computing Facility
- eDIKT initiative
- EPSRC [EP/E035469/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/E035469/1] Funding Source: researchfish
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We prepared the complexes [Ru{4,4`-(CO2R-bpy)(2)}{Cu(exoO(2)-cyclam)}][NO3](2) [R = Et (1), H (2)], which possess a Cu-II centre covalently linked to a (bipyridyl)Ru-II fragment. The complexes were characterised by cyclic voltammetry, UV/Vis spectroscopy, hybrid DFT and TD-DFT (time-dependent density-functional theory) calculations, EPR (electron paramagnetic resonance), emission spectroscopy and UV/Vis spectroelectrochemistry, with the latter showing reversible conversion to the mono- and di-oxidised and mono- and di-reduced species. The data suggest the first oxidation to be largely based on the Ru centre but with little energetic difference between the highest occupied orbitals based on Ru and based on Cu. There was also evidence of solvent co-
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