Subcomponent self-assembly allows the construction of complex architectures from simple building blocks via formation of covalent bonds around metal templates. Since both covalent and coordinative bonds are formed reversibly, a wealth of rearrangement reactions is possible involving substitution at both intraligand (often C==N) and metal-ligand (N -> metal) bonds. If the possibilities latent within a set of subcomponents and metal ions are understood, one may also select specific structures from among dynamic libraries of products. The parallel preparation of structures from “nonorthogonal” mixtures of subcomponents is also possible, as is the direction of subcomponents to specific sites within product structures.