Covalent Post-Assembly Modification: A Synthetic Multipurpose Tool in Supramolecular Chemistry

The use of covalent post-assembly modification (PAM) in supramolecular chemistry has grown significantly in recent years, to the point where PAM is now a versatile synthesis tool for tuning, modulating, and expanding the functionality of self-assembled complexes and materials. PAM underpins supramolecular template-synthesis strategies, enables modular derivatization of supramolecular assemblies, permits the covalent 'locking' of unstable structures, and can trigger controlled structural transformations between different assembled morphologies. This Review discusses key examples of PAM spanning a range of material classes, including discrete supramolecular complexes, self-assembled soft nanostructures and hierarchically ordered polymeric and framework materials. As such, we hope to highlight how PAM has continued to evolve as a creative and functional addition to the synthetic chemist's toolbox for constructing bespoke self-assembled complexes and materials.