In this contribution, we discuss the use of simple pyrimidine derivatives and geometrically related heterocycles in combination with protected metal ions to build cyclic polynuclear coordination assemblies. The resulting assemblies range from conformationally rigid triangles to corrugated octagons with positively charged cavities and surfaces that can interact with anionic species in a supramolecular fashion. Special attention has been focussed to the supramolecular interaction of these systems towards mononucleotides and DNA as a possible novel interaction of DNA binding metallo-drugs. The results show that these systems efficiently interact with both mononucleotides and ds-DNA. The molecular recognition of ds-DNA leads to significant conformational changes, however, this interaction gives only rise to moderate cytotoxic effects towards tumour cell lines.