Interaction of Ruthenium(II)-dipyridophenazine Complexes with CT-DNA: Effects of the Polythioether Ancillary Ligands

摘要

The complexes [Ru([9]aneS3)(dppz)Cl]Cl 1 and [Ru([12]aneS4)(dppz)]Cl2 2 ([9]aneS3 = 1,4,7- trithiaciclononane and [12]aneS4 = 1,4,7,10-tetrathiaciclododecane) were synthesised and fully characterised. These complexes belong to a small family of dipyridophenazine complexes with non-polypyridyl ancillaryligands . Interaction studies of these complexes with CT-DNA (UV/Vis titrations, steady-state emission andthermal denaturation) revealed their high affinity for DNA . Intercalation constants determined by UV/Vistitrations are of the same order of magnitude (106) as other dppz metallointercalators, namely[Ru(II)(bpy)2dppz]S2+. Differences between l and2 were identified by steady-state emission and thermal denaturation studies . Emission results are in accordance with structural data, which indicate how geometricdistortions and different donor and/or acceptor ligand abilities affect luminescence. The possibility of noncovalentinteractions between ancillary ligands and nucleobases by van der Waals contacts and H-bridges isdiscussed . Furthermore, complex l undergoes aquation under intra-cellular conditions and an equilibriumwith the aquated form l' is attained . This behaviour may increase the diversity of available interactionmodes.