Metal-coordination-driven dynamic heteroleptic architectures

Dynamic heteroleptic coordination at metal centres is quite common in Nature and often related to a specific biological function, such as in zinc finger proteins and in hemoglobin for oxygen transport. To achieve the required high heteroleptic fidelity, representative biological systems avail themselves of "intramolecular" multidentate coordination using the protein backbone as a "superligand". In contrast, dynamic heteroleptic coordination at a single metal centre in solution requires to bind different freely exchanging ligands under thermodynamic control. In this tutorial review we present the emerging principles of how to assemble dissimilar ligands at dynamically exchanging metal centres, with a particular emphasis on using the precepts for the fabrication of heteroleptic supramolecular assemblies in solution.