Journal
INORGANICA CHIMICA ACTA
Volume 362, Issue 14, Pages 4953-4959Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2009.07.035
Keywords
Ru(II) complexes; Electropolymerization; Photosensitization; DFT calculations
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Funding
- Natural Sciences and Engineering Research Council
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One-step syntheses are reported of 4'-(pyrrol-2-yl)-2,2'; 6',2 ''-terpyridine, 4-(pyrrol-2-yl)-2,6-di(pyrazol-2-yl)pyridine and of their homoleptic Ru(II) complexes, in good to very good yields. DFT calculations con. firmed that the pyrrole rings lay coplanar with the tridentate cores and constituted effective pi-donors, but also showed that the properties of the Ru(II) complexes defied classical analyses based on localized metal- or ligand-centred orbitals. The low-potential electrochemical oxidations led to electropolymerization but were not purely pyrrole-centred. The low-energy electronic spectral absorptions were not purely metal-to-ligand charge transfer (MLCT) in character, but resulted from mixed metal- to-ligand and intraligand transitions. The complexes' photosensitization abilities showed that the pyrrole groups were beneficial to the survival of the photoexcited states, albeit not as much as p-tolyl groups. (c) 2009 Elsevier B.V. All rights reserved.
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