title: [Ru(TAP)2(dppz)]2+: a DNA intercalating complex, which luminesces strongly in water and undergoes photo-induced proton-coupled electron transfer with guanosine-5'-monophosphate.
abstract: The lowest excited state of [Ru(TAP)2(dppz)]2+ (TAP = 1,4,5,8-tetraazaphenanthrene, dppz = dipyrido[3,2-a:2',3'-c]phenazine) 1 is strongly luminescent, even in water, and very oxidizing. Therefore it is able to oxidise not only guanosine-5'-monophosphate (GMP), as demonstrated by laser flash photolysis, but also guanine-containing polynucleotides such as calf thymus DNA and [poly(dG-dC)]2. The luminescence quenching was found to be faster in H2O than in D2O, as is the back reaction, indicating that both processes probably proceed by proton-coupled electron transfer. These properties, that are controlled by the triplet MLCT state in which the charge has been transferred from the Ru to a TAP ligand, contrast with those of the well known [Ru(phen)2(dppz)]2+ 2.
authors.affiliation: Service de Chimie Organique et Photochimie, CP 160/08, Université Libre de Bruxelles, 50 Avenue F. D. Roosevelt, B-1050 Bruxelles, Belgium.
authors.forename: Isabelle
authors.initials: I
authors.lastname: Ortmans
authors.forename: Benjamin
authors.initials: B
authors.lastname: Elias
authors.forename: John M
authors.initials: JM
authors.lastname: Kelly
authors.forename: Cécile
authors.initials: C
authors.lastname: Moucheron
authors.forename: Andrée
authors.initials: A
authors.lastname: Kirsch-DeMesmaeker
mesh_terms: D004247:DNA / Q000737:chemistry*; D004563:Electrochemistry; D006157:Guanosine Monophosphate / Q000737:chemistry*; D007364:Intercalating Agents / Q000737:chemistry*; D008163:Luminescent Measurements / Q000379:methods; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D010777:Photochemistry; D011522:Protons; D012428:Ruthenium / Q000737:chemistry*; D014867:Water / Q000737:chemistry
chemical_list: D007364:Intercalating Agents; D009942:Organometallic Compounds; D011522:Protons; D014867:Water; D012428:Ruthenium; D006157:Guanosine Monophosphate; D004247:DNA