Résumé : The properties that are characteristic of TAP (1,4,5,8- tetraazaphenanthrene) and HAT (1,4,5,8,9,12-hexaazatriphenylene) RuII complexes under illumination are highlighted and compared with those of other metallic complexes. In particular, the photo-oxidizing power of their 3MLCT states leads to a quenching of luminescence accompanied by a photoreaction when they are in presence of nucleic acids. The proton-coupled photoinduced electron transfer with the guanine nucleobases produces metallic adducts on DNA guanine units. The mechanism of formation, structure, and possible applications of these photoadducts are discussed and compared with other DNA metallic adducts currently in the literature. © Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.