A survey of the contemporary challenges of the field of unsubstituted group 15 element ligand complexes (excluding N) is given. The focus of the article is on the coordination chemistry behaviour of such En ligand complexes. This field is subdivided into two areas of reactivity: En ligand complexes with (i) noncoordinated Lewis-acidic cations and (ii) Lewis-acidic coordination compounds containing at least one permanently coordinating ligand. In the latter case, insoluble 1D and 2D polymers respectively are obtained; however, under special conditions soluble, spherical, fullerene-like giant molecules are formed. These nano-sized molecules are up to 2.4 nm in diameter and are able to encapsulate small molecules in their holes. In contrast, the first-mentioned field uses weakly coordinating anions to obtain readily soluble di- and polycationic products. These show depolymerisation tendencies in solution under the formation of oligomer–monomer equilibria and thus reveal dynamic supramolecular aggregation processes.