A range of metal thioether macrocyclic complexes has been used as templating agents in the preparation of extended multi-dimensional polyiodide arrays. A selection of unusual and intriguing polyiodides is described, and the role played by the size, shape and charge of the metal macrocyclic complex discussed.

In this tutorial review, we will discuss the most significant achievements in the structure-based design of cyclic receptors containing mainly aliphatic amine groups as metal-free hosts for phosphate-based guests in aqueous environment; in particular, inorganic phosphates and mononucleotide anions. The bulk of our attention will be devoted to show how this class of receptors has structurally evolved following the attempts by chemists to optimize all factors indicated by Nature as necessary to achieve the best possible binding of phosphates via non-covalent interactions.