Structural Investigation into the Threading Intercalation of a Chiral Dinuclear Ruthenium(II) Polypyridyl Complex through a B‑DNA Oligonucleotide

Herein we report the separation of the three stereoisomers of the DNA light-switch compound [{Ru­(bpy)2}2(tpphz)]4+ (tpphz = tetrapyrido­[3,2-a:2′,3′-c:3″,2″-h:2‴,3‴-j]­phenazine) by column chromatography and the characterization of each stereoisomer by X-ray crystallography. The interaction of these compounds with a DNA octanucleotide d­(GCATATCG).d­(CGATATGC) has been studied using NMR techniques. Selective deuteration of the bipyridyl rings was needed to provide sufficient spectral resolution to characterize structures. NMR-derived structures for these complexes show a threading intercalation binding mode with slow and chirality-dependent rates. This represents the first solution structure of an intercalated bis-ruthenium ligand. Intriguingly, we find that the binding site selectivity is dependent on the nature of the stereoisomer employed, with Λ RuII centers showing a better intercalation fit.