Selective triflate to chlorine ligand exchange reaction between ditriflate and dichloride Pt complexes producing pure heterosubstituted complexes is demonstrated. We show that this reaction can be applied for selective chlorination of supramolecules leading to their structural transformation into multinuclear mono-chlorinated Pt(II) complexes. The X-ray structure of complex of 4,4'-bipyridine with two molecules of (Et(3)P)(2)Pt(Cl)OTf is reported.