The scope of application of macrocyclic polyamines beyond metal chelation

Recent advances in the use of radiometals for both imaging and therapy has spurred on the development of an original chemistry that endows radionuclide-chelating molecular cages with ever sharper physicochemical properties. Macrocyclic polyamines (MPAs) such as cyclen and DOTA are among the most frequently encountered cages for the design of new radiotracers, owing to their versatile chemistry that makes them customizable molecular tools. The idea of using MPAs for alternative purposes has recently emerged, with an eye towards benefiting from their unique topology, versatility, symmetry and water-solubility. This review summarizes strategies that have been recently implemented in which MPAs are used as multivalent molecular platforms for constructing sophisticated suprastructures that found applications in various fields, from material chemistry to chemical biology. These original approaches are invaluable in that they successfully expand the scope of applications of MPAs far beyond their restricted roles of metal chelating appendages.