1. Ground vs. excited state interaction in ruthenium-thienyl dyads
- Author
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Noel M. O'Boyle, John J. McGarvey, William Henry, Wesley R. Browne, Kate L. Ronayne, Johannes G. Vos, Stratingh Institute of Chemistry, and Synthetic Organic Chemistry
- Subjects
Triazole ,ELECTROCHEMICAL PROPERTIES ,chemistry.chemical_element ,LMCT ,EFFECTIVE CORE POTENTIALS ,Analytical Chemistry ,Inorganic Chemistry ,chemistry.chemical_compound ,CHARGE-TRANSFER TRANSITIONS ,TRIS(BIPYRIDINE)RUTHENIUM(II) ,Computational chemistry ,Thiophene ,ruthenium ,thienyl ,HOMO/LUMO ,Raman ,Spectroscopy ,POLYPYRIDYL COMPLEXES ,OS(III) COMPLEXES ,Ligand ,Organic Chemistry ,MOLECULAR CALCULATIONS ,charge transfer states ,Ruthenium ,chemistry ,Superexchange ,Excited state ,PHOTOPHYSICAL PROPERTIES ,Polar effect ,METAL-COMPLEXES ,LIGAND - Abstract
The vibrational and photophysical properties of mononuclear ruthenium(II) and ruthenium(III) polypyridyl complexes based on the, ligands 2-(5-(pyridin-2"-yl)-1'H-1',2',4'-triaz-3'-yl)-thiophene, 2-(5-(pyrazin-2"-yl)-1'H-1',2,4-triaz-3'-yl)-thiophene, are reported. The effect of the introduction of the non-innocent thiophene group on the properties of the triazole based ruthenium(II) complex is examined. The pH sensitive 1,2,4-triazole group, although influenced by the electron withdrawing nature of the thiophene group, does not facilitate excited state interaction of the thiophene and Ru(II) centre. Deuteriation and DFT calculations are employed to enable a deeper understanding of the interaction between the two redox-active centres and rationalise the difference between the extent of ground and excited state interaction in this simple dyad. The results obtained provide considerable evidence in support of earlier studies examining differences in ground and excited state interaction in multinuclear thiophene-bridged systems, in particular with respect to HOMO- and LUMO- mediated superexchange interaction processes. (C) 2004 Elsevier B.V. All rights reserved.
- Published
- 2005