Abstract
Constitutional dynamic chemistry (CDC) expressing the adaptive dynamic behaviors of both molecular and supramolecular systems potentially facilitates their self-evolution toward a selection of discrete systems from mixtures of objects reversibly exchanging and continuously reorganizing at the nano- or macroscopic levels. This chapter focuses on the implementation of constitutional dynamic chemistry principles to build dynamic constitutional metallosupramolecular systems. The basic working principles of emerging metallosupramolecular architectures are provided to better understand the requirements in system structural self-selection for the generation of functional systems. Single or double level dynamic metallosupramolecular libraries (DMLs) can be generated via metal-ligand and reversible covalent ligand bond exchanges. The metal ion coordination process may position ligands in close proximity to one another. Such proximity potentially facilitates synergistic reversible molecular exchanges and supramolecular non-covalent interactions, thereby leading to the rearrangements of the coordinating ligands within a restricted interactional space defined by the coordination geometry around the metal centers. Actual and potential applications of such systems are presented.