Syntheses and properties of bimetallic chromophore-quencher assemblies containing ruthenium(II) and rhenium(I) centers

Benjamin J. Coe, Naomi R M Curati, Emma C. Fitzgerald, Simon J. Coles, Peter N. Horton, Mark E. Light, Michael B. Hursthouse

    Research output: Contribution to journalArticlepeer-review


    We have prepared a family of six new bimetallic complexes containing electron-donating trans-[RuII-Cl(pdma)2}+ [pdma = 1,2-phenylenebis(dimethylarsine)] centers linked to trans-[Ru IICl(pdma)(2,2′-bpy)-(NO)] (bpy = bipyridyl) or fac-{Re I(biq)(CO)3}+-based (biq = 2,2′- biquinolinyl) electron acceptors. The extended bridging units are based on 4,4′-bpy or bpe [E-1,2-bis(4-pyridyl)ethylene] ligands, and these assemblies are designed to display long-lived photoinduced charge-separated states. A number of new monometallic precursor complexes have also been synthesized and fully characterized. The electronic absorption spectra of the bimetallic species are dominated by intense, visible d(RuII) → πr*(4,4′-bpy/bpe) metal-to-ligand charge-transfer (MLCT) bands and d(ReI) → π*(biq) absorptions in the near-UV region. Cyclic voltammetric studies show both metal-based oxidation and ligand-based reduction processes and provide evidence that these assemblies contain thermodynamic driving, forces for charge separation. Single-crystal X-ray structures have been determined for the monometallic complex salts fac-[Re I(biq)-(CO)3(MeCN)]CF3SO3· CHCl3, /ac-[ReI(biq)(CO)3(4-BrCH 2C5H4N)]PF6, fac-[Re I(biq)(CO)3(4-HCO2-CH2C 5H4N)]PF6·Me2CO, fac-[Re I(biq)(CO)3(ISNE)]CF3SO3 (ISNE = ethylisonicotinate), and fac-[ReI(biq)(CO)3(NC 5H4CO2)]2·HPF 6·3MeCN. Ultrafast time-resolved infrared and Raman spectroscopic measurements will be employed to investigate the photoexcitation properties of the bimetallic species and of monometallic reference complexes. © 2007 American Chemical Society.
    Original languageEnglish
    Pages (from-to)2318-2329
    Number of pages11
    Issue number9
    Publication statusPublished - 23 Apr 2007


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