Simple thermodynamics for unravelling sophisticated self-assembly processes.

During the past 15 years, coordination chemistry has rapidly developed toward multicomponent assemblies involving several ligands and metal ions, which are connected via intra- or intermolecular processes. The fascinating structural aspect of these complexation reactions has been early recognized for the design of sophisticated (supra)molecular architectures with novel topologies and functions, while the concomitant energetic part only recently emerged as a potential tools for controlling and programming self-assemblies. In this Perspective, we focus on the modelling of the free energy changes accompanying self-assembly processes. Starting with the original protein-ligand model borrowed from biology, which describes complicated multicomponent assemblies, we present (i) its adaptation to coordination chemistry and (ii) its significance for addressing cooperativity as an extra energy cost resulting from intercomponent interactions. An additional entropic concept arising from the separation of intra- and intermolecular complexation processes is then discussed, together with its explicit consideration for modeling multicomponent complexation reactions. Finally, both aspects (i.e. cooperativity and intra-/intermolecular connections) are combined in the extended site binding model, which is able to dissect free energy changes occurring in sophisticated metal-ligand assemblies with a minimum set of microscopic parameters. Applications to experimental complexation reactions of increasing complexity are systematically discussed, and illustrate the potential and limitations of each model.