The interaction of the complexes [Pt(bipy)(4-Rpy)(2)](2+) and [Pt(4,4'-Ph(2)bipy)(4-Rpy)(2)](2+) (Ph = phenyl; bipy = 2,2'-bipyridine; R = H, CN, CH3, NH2) with DNA has been studied with a series of techniques. The processes give rise to (i) lengthening of rodlike DNA and unwinding of closed circular DNA and (ii) an increase in the DNA melting temperature comparable with that observed for known intercalators. In addition, the reaction of the complexes [Pt(bipy)(py)(2)](2+) and [Pt(4,4'-Ph(2)bipy)(py)(2)](2+) is inhibited by the presence of DNA. These results have been interpreted by assuming that the substances intercalate-in spite of the presence of ligands out of plane. The crystal structure determined for [Pt(4,4'-Ph(2)bipy)(3,5-Me(2)py)(2)](2+) by X-ray analysis shows that also one of the phenyl rings is twisted with respect to the square plane. Binding constants, K-B, determined spectrophotometrically at 25 degrees C and pH 7 using the McGhee-von Kippel approach, increase for both series of complexes on increasing pK(a) of coordinated pyridines and are larger for those with 4,4'-Ph(2)bipy. The increasing affinity for DNA on increasing electron density of the interacting moiety is accounted for by assuming that London dispersion forces play a major role in the processes.