Organometallic polyphosphorus complexes as diversified building blocks in coordination chemistry

Abstract The complexes containing cyclo-Pn ligands which are π-coordinated to a metal atom have been known since the late 1970 s. Cyclo-Pn ligands being cyclic aromatic P-donors represent a class of non-carbon ligands that are able to coordinate Lewis acidic metal cations by a single P donor atom or by an aromatic P-P bond. This ability allows to use them as rigid multidentate building blocks for coordination-driven self-assembly leading to products of different complexity from discrete polynuclear complexes to infinite multidimensional coordination polymers and giant supramolecules up to 4.6 nm in size that can also be united into a coordination network. Depending on the number and position of phosphorus atoms of the Pn ring, different coordination modes can be realized. The structural diversity of the self-assembled architectures arises not only from the variety of the coordination modes of the cyclo-Pn ligand, but also from the combinations of these modes in one compound. In this review, the interrelation between coordination and the resulting structural motifs occurred in all so far reported cyclo-Pn ligand complexes is comprehensively discussed and the factors which influence the metallosupramolecular architecture of the compounds are outlined for every class of cyclo-Pn ligand complexes with given n (n = 3–6).