Preparation and properties of ruthenium (II) complexes of 2,2′:6′,2″-terpyridines substituted at the 4′-position with heterocyclic groups

Abstract: Four ligands whose general formula is R-terpy with terpy=2,2′:6′,2″ terpyridine bearing at the 4′-position a substituent R=2-furyl, 2-pyrrolyl, 2-thienyl and 5-2,2′bithienyl were synthesised. The absorption spectra and the electrochemical behaviour of the corresponding homoleptic Ru(II) complexes were investigated and compared to those of the parent complex [Ru(terpy)]2+. Due to the donor effect of the grafted heterocyclic groups, the absorption and emission maxima are red-shifted and the energy levels of the HOMO Π(t2g) metal orbitals are slightly higher. The incorporation of these heterocyclic moieties extends the electronic delocalisation over the corresponding ligands, leading to higher emission quantum yields. Cyclic voltammetric studies of pyrrolyl-, thienyl- and bithienyl-functionalised complexes show that an electroactive layer can be deposited on the electrode. Preliminary results point out that an electrodeposited film could be used as a photocathode in an aqueous electrolyte. [Copyright &y& Elsevier]