Assessment of intercomponent interaction in phenylene bridged dinuclear ruthenium(II) and osmium(II) polypyridyl complexes |
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Authors: | Guckian Adrian L Doering Manfred Ciesielski Michael Walter Olaf Hjelm Johan O'Boyle Noel M Henry William Browne Wesley R McGarvey John J Vos Johannes G |
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Institution: | National Centre for Senior Research, School of Chemical Sciences, Dublin City University, Glasnevin, Dublin 9, Ireland. |
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Abstract: | The synthesis and characterisation of Ru(bipy)(2)(L1)](2+) and the homodinuclear complexes M(bipy)(2)(L1)M(bipy)(2)](4+)(where M = Ru or Os), employing the ditopic ligand, 1,4-phenylene-bis(1-pyridin-2-ylimidazo1,5-a]pyridine)(L1), are reported. The complexes are identified by elemental analysis, UV/Vis, emission, resonance Raman, transient resonance Raman and (1)H NMR spectroscopy, mass spectrometry and electrochemistry. The X-ray structure of the complex Ru(bipy)(2)(L1)(bipy)(2)Ru](PF(6))(4) is also reported. DFT calculations, carried out to model the electronic properties of the compounds, are in good agreement with experiment. Minimal communication between the metal centres is observed. The low level of ground state electronic interaction is rationalized in terms of the poor ability of the phenyl spacer in facilitating superexchange interactions. Using the electronic and electrochemical data a detailed picture of the electronic properties of the RuRu compound is presented. |
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