ABSTRACT
This review focuses on recent advances in the field of main‐group supramolecular coordination chemistry, highlighting specific examples where a main‐group ion serves as the directing element for the self‐assembly of a discrete cluster. The review focuses on assemblies that have been structurally characterized and, when reported, describes the solution persistence and speciation of the discrete species. This entry is organized around the p‐block of the periodic table, with sections devoted to Group 12–17 chemistry. “Coordination” preferences, geometry, and ligand substitution dynamics of the main‐group ions are described with an eye toward developing predictive design strategies featuring the main‐group ions in supramolecular self‐assembly. This review shows that the unusual coordination chemistry of the main‐group ions has provided supramolecular chemistry with novel assemblies, new hosts possessing endohedrally functionalized cavities, and unusual new dynamic covalent reactivity.
