This paper describes redox chemistry in semisolid molten salts ionic liquids of DNA in which the counterions of the phosphates are redox-active metal complexes with bipyridine ligands labeled with MW 350 poly(ethylene glycol) (PEG) "tails", e.g., M(bpY(350))(3)DNA (where M = Co, Ni, and bpy(350) = 4,4'-(CH3(OCH2-CH2)(7)OCO)(2)-2,2'-bipyridine). Other redox-active metal complexes are added to the M(bpy(350))(3)DNA melt: (a) the PEG-tailed metal bipyridine complexes Fe(bpy(350))(3)(ClO4)(2) and Ru(bpy(350))(3)(ClO4)(2) and (b) the nontailed complexes Os(bpy)(3)CI2 (bpy = 2,2'-bipyridine) and Os(bpy)(2)dppzCl(2) (dppz = dipyridophenazine). In example a, electrogeneration of the powerful oxidizers [Fe(bpy(350))(3)](3+) and [Ru(bpy(350))(3)](3+) gives microelectrode voltammetry indicative of electrocatalytic oxidation of DNA base sites. Since physical diffusion of the metal complexes is slow in the viscous semisolids (and that of DNA is nil), the rate of electron hopping between the base sites of the DNA becomes a significant contributor to the overall charge transport rate, as deduced from analysis of the voltammetry. DNA base site self-exchange rate constants of 1.1 x 10(6) and 1.8 x 10(6) s(-1) are estimated from measurements using Fe(bpy(350))(3)(3+) and Ru(bpy(350))(3)(3+) oxidants, respectively. In example b, a complex known to be a DNA intercalator in aqueous solutions is found to not be an intercalator in the DNA molten salt environment, as deduced from measurements showing the physical diffusion coefficients of aqueous nonintercalator Os(bpy)(3)Cl-2 and aqueous intercalator Os(bpy)(2)dppzCl(2) to be indistinguishable in the M(bpy(350))(3)DNA melt.