Supramolecular Matter Through Crystal Engineering: Covalent Bond Formation to Postsynthetic Modification

Supramolecular chemistry can transform organic synthesis by revealing that crystalline materials are not static but rather dynamic environments for controlled covalent bond formations and manipulations. This review focuses on how supramolecular chemistry can be developed to direct molecular synthesis in the organic solid state, directing reliable C─C bond formations to enable transformations difficult or impossible in solution. Special attention is given to postsynthetic modifications that serve to broaden the functional scope of solid-state reactivity allowing organic crystals to be developed as molecular flasks and a form of supramolecular matter.