DNA Sequence and Ancillary Ligand Modulate the Biexponential Emission Decay of Intercalated [Ru(L)2dppz]2+ Enantiomers

Journal article, 2012

The bi-exponential emission decay of [Ru(L)2dppz]2+ (L=N,N'-diimine ligand) bound to DNA has been studied as a function of polynucleotide sequence, enantiomer, and nature of L (phenanthroline vs. bipyridine). The lifetimes (ti) and pre-exponential factors (ai) depend on all three parameters. With [poly(dA-dT)]2, the variation of ai with [Nu]/[Ru] has little dependence on L for ?-[Ru(L)2dppz]2+ but a substantial dependence for ?-[Ru(L)2dppz]2+. With [poly(dG-dC)]2, by contrast, the ?-enantiomer ai values depend strongly on the nature of L, whereas those of the ?-enantiomer are relatively unaffected. DNA-bound linked dimers show similar photophysical behaviour. The lifetimes are identified with two geometries of minor-groove intercalated [Ru(L)2dppz]2+, resulting in differential water access to the phenazine nitrogen atoms. Interplay of cooperative and anti-cooperative binding resulting from complexcomplex and complexDNA interactions is responsible for the observed variations of ai with binding ratio. [Ru(phen)2dppz]2+ emission is quenched by guanosine in DMF, which may further rationalise the shorter lifetimes observed with guanine-rich DNA.