Crystal engineering of coordination networks: Then and now

Coordination networks are a structurally and compositionally diverse class of network solid which are amenable to crystal engineering by exploiting the interactions and symmetry of the underlying metal centers (nodes) and organic (and/or inorganic) ligands that connect these centers (linkers). Herein, we detail how crystal engineering of coordination networks has evolved from its initial focus upon the development of design principles to its current focus upon gaining a better understanding of structure/function relationships to improve performance. The primary focus herein is the delineation of those design principles that are now well established, in particular the following: the node-and-linker approach to network design; the propensity of certain metals to form molecular building blocks or supermolecular building blocks that are robust enough to be used across a range of metals and linkers; and the utility of topological analysis to generate blueprints for families of related materials. The properties of the resulting coordination networks, and crystal engineering thereof, are addressed through case studies. This chapter may serve as an introductory guide to the state of the art of crystal engineering as it applies to coordination networks.