[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

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 lase...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2004-02 (4), p.668-676
Main Authors: Ortmans, Isabelle, Elias, Benjamin, Kelly, John M, Moucheron, Cécile, Kirsch-DeMesmaeker, Andrée
Format: Article
Language:English
Subjects:
DNA - chemistry
Electrochemistry
Guanosine Monophosphate - chemistry
Intercalating Agents - chemistry
Luminescent Measurements - methods
Molecular Conformation
Organometallic Compounds - chemical synthesis
Organometallic Compounds - chemistry
Oxidation-Reduction
Photochemistry
Protons
Ruthenium - chemistry
Water - chemistry
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Summary: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.
ISSN:1477-9226
1477-9234
DOI:10.1039/b313213g