Article révisé par les pairs
Résumé : The design of RuII complexes photoreactive with biomolecules represents an important target for the development of novel photoprobes for the study of DNA and proteins, and for the production of novel metal-based potential therapeutic agents. Luminescent RuII complexes based on π-accepting ligands were designed to allow a photoreactivity towards biomolecules, thanks to their important photo-oxidizing power. It was clearly demonstrated that this photoreactivity originates from a primary photo-induced electron transfer (PET) process from either a guanine moiety (G) or a tryptophan residue (Trp) to the excited complex. One of the consequences of this PET process is the formation of a photoadduct between the RuII complex and the G or Trp moieties of a biomolecule. In those photoadducts a covalent bond is formed linking the biomolecule to one ligand of the complex without destruction of the chelation sphere around the metal ion. These photoadducts can be exploited to photocrosslink two complementary oligonucleotides (ODNs), two peptides or even a single ODN with a peptide. Such photocrosslinking could be exploited either for diagnostic purposes or for therapeutic applications.We review in this work the advances to date in the understanding of the primary processes responsible for the photoadduct formation and we show how this photochemical behavior can be exploited for applications with DNA, peptides and proteins.