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The binding properties and sequence selectivities of - and (bip = 4,4'-biphenylene (imidazo [4,4-f][1,10]phenanthroline) complexes with and were investigated using conventional spectroscopic methods. When bound to , a large positive circular dichroism (CD) spectrum was induced in absorption region of the bridging moiety for both the - and complexes, which suggested that the bridging moiety sits in the minor groove of the polynucleotide. As luminescence intensity increased, decay times became longer and complexes were well-protected from the negatively charged iodide quencher compared to that in the absence of . These luminescence measurements indicated that Ru(II) enantiomers were in a less polar environment compared to that in water and supported by minor groove binding. An angle of between the molecular plane of the bridging moiety of the complex and the local DNA helix axis calculated from reduced linear dichroism () spectrum further supported the minor groove binding mode. In the case of complex, this angle was , suggesting a tilt of DNA stem near the binding site and bridging moiety sit in the minor groove of the . In contrast, neither -nor complex produced significant CD or signal in the absorption region of the bridging moiety. Luminescence measurements revealed that both the - and complexes were partially accessible to the quencher. Furthermore, decay times became shorter when bis-Ru(II) complexes bound to . These observations suggest that both the - and complexes bind at the surface of , probably electrostatically to phosphate group. The results indicate that - and are able to discriminate between AT and GC base pairs.

Sequence Dependent Binding Modes of the ΔΔ- and ΛΛ-binuclear Ru(II) Complexes to poly[d(G-C)2] and poly[d(A-T)2]

Sequence Dependent Binding Modes of the ΔΔ- and ΛΛ-binuclear Ru(II) Complexes to poly[d(G-C)₂] and poly[d(A-T)₂]