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Bis(R-bipyridyl)ruthenium bibenzimidazole complexes (R = H, Me or Bu'): Supramolecular arrangement via hydrogen bonds, photo- And electro-chemical properties and reactivity towards carbon dioxide

par Rau, Sven;Rüben, Mario;Büttner, Torsten;Temme, Christian;Dautz, Sylvana;Görls, Helmar;Rudolph, Manfred;Walther, Dirk;Brodkorb, André ;Duati, Marco;O'Connor, Christine;Vos, Johannes G.
Référence Journal of the Chemical Society, Dalton Transactions, 20, page (3649-3657)
Publication Publié, 2000

Article révisé par les pairs

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Résumé :

Complexes of the type [Ru(H2bibzim)(R-bpy)2X2-nH2O (R = H, 2,2′-bipyridine, bpy, X = CF3SO3- 1; R = Me, 4,4′-dimethyl-2,2′-bipyridine, dmbpy, X = PF6- 2; R = tert-buiyl, 4,4′-di-/e/7-butyl-2,2′-bipyridine, tbbpy, X = CI- 3; Hjbibzim = l,l′-bibenzimidazole) containing two NH functions acting as hydrogen bond donors formed different spatially highly organised supramolecular assemblies with water. X-Ray investigation revealed that the nature of the counter ion influences the hydrogen bonding pattern and extent of spatial organisation. In 2 one dimensional chains of hydrogen bonded water could be found. In the deprotonated complex [Ru(bibzim)(tbbpy)2] 4 water molecules serve as hydrogen bond donors. The diastereomeric forms 5a/5b of the homodinuclear ruthenium complex [{Ru(tbbpy)2}2(bibzim)][PF6]2 could be separated. No differences in their photophysical properties could be detected. The X-ray investigation of 5a and [{Ru(bpy)2}2(bibzim)][PF6]2 6 showed little influence of peripheral substitution on structural properties. Complexes 3-5 exhibit activity in electrochemical CO2 reduction which can be tuned by variation of the degree of protonation of the bibenzimidazole. ©The Royal Society of Chemistry 2000.