Résumé : A series of 17-mer oligonucleotides labeled with [Ru(tap)2(dip)]2+ (tap = 1,4,5,8-tetraazaphenanthrene; dip = 4,7-diphenylphenanthroline) at position 5 of an uracil residue in the middle of the sequence (e.g. see scheme) have been prepared and characterized. The luminescence of the chemically attached complex is quenched by hybridization with the complementary sequence, when it contains guanines in the vicinity of the Ru site. This electron-transfer quenching process generates a photoproduct on the illuminated duplex, that is responsible for an irreversible photocrosslinking of the two strands.