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 templatesynthesis 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, selfassembled 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.

High surface area carbon coatings are produced by plasma‐enhanced chemical vapour deposition using a high‐voltage dielectric barrier discharge under conditions where aggregates are formed in the plasma and the growing coating is subjected to plasma immersion ion implantation. We extend the Smoluchowski aggregation theory to include the continuous production of monomers to explain the observed microstructure of the coatings as a function of the pressure of deposition. The larger particles show evidence of the accretion of monomers on their surfaces with characteristic voids resulting from island growth. The coatings are subjected to plasma immersion ion implantation using high‐voltage pulses that create radicals for binding biomolecules. The increased surface area by the presence of the aggregated particles binds a significantly higher amount of protein than smooth coatings, making them potentially useful for electrodes, biosensing and drug delivery.