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.

Dissipative self-assembly leads to structures and materials that exist away from equilibrium by continuously exchanging energy and materials with the external environment. Although this mode of self-assembly is ubiquitous in nature, where it gives rise to functions such as signal processing, motility, self-healing, self-replication, and ultimately life, examples of dissipative self-assembly processes in man-made systems are few and far between. Herein, recent progress in developing diverse synthetic dissipative self-assembly systems is discussed. The systems reported thus far can be categorized into three classes, in which: i) the fuel chemically modifies the building blocks, thus triggering their self-assembly, ii) the fuel acts as a template interacting with the building blocks noncovalently, and iii) transient states are induced by the addition of two mutually exclusive stimuli. These early studies give rise to materials that would be difficult to obtain otherwise, including hydrogels with programmable lifetimes, vesicular nanoreactors, and membranes exhibiting transient conductivity.

Over years, mathematicians, biologists and chemists have capitalised on the highly useful concept of orthogonality for developing sophisticated complex systems. The use of orthogonal pairs ensures that any modification made on one pair does not propagate any effect onto the other. While the concept equally pertains to dynamic supramolecular interactions, interference-free self-assembly built on multiple orthogonal interactions is still limited and the underlying notions are not yet firmly established. Herein, we identify, classify and evaluate dynamic interactions in various orthogonal settings in order to distill out general recommendations for reliable dynamic orthogonality. Our classification has to exclude templating, allosteric and/or cooperative effects as the latter are specific for individual cases only.