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.

Post-polymerization CuAAC reactions are used to ‘click’ stimuli-cleavable triazole end-caps onto self-immolative poly(ethyl glyoxylate).

Self-immolative linkers offer efficient mechanisms for deprotecting 'caged' functional groups in response to specific stimuli. Herein we describe a convenient 'click' chemistry method for introducing pendant self-immolative linkers to a polymer backbone through post-polymerization modification. The intro duced triazole rings serve both to anchor the stimuli-cleavable trigger groups to the polymer backbone, while also forming a functional part of the selfimmolation cascade. We investigate the polymerization kinetics, postsynthetic modification, and self-immolation mechanism of a model polymer system, and discuss avenues for future studies on polypendant self-immolative triazoles as a modular, stimuli-responsive macromolecule platform.

Synthetic polymers are well known to self-assemble into a wide range of remarkable architectures with properties directly arising from their nanoscale morphologies. The rapid development of post-polymerisation modification reactions and techniques like polymerisation induced self-assembly (PISA) have fuelled new research into ‘smart’ polymer assemblies that can undergo well defined morphological transformations in response to external stimuli. These transformations can be used to modulate the properties of polymer assemblies in a ‘switchable’ fashion, offering great potential to generate smart materials that can dynamically adapt to changes in complex environments. This review aims to highlight key developments from the past five years in this rapidly evolving field, and we discuss innovations in polymer design, stimuli-responsivity mechanisms, transformation behaviours, and potential applications of shape-transformable polymeric nanostructures.

<div> <div> <div> <p>Self-immolative linkers offer efficient mechanisms for deprotecting ‘caged’ functional groups in response to specific stimuli. Herein we describe a convenient ‘click’ chemistry method for introducing pendant self-immolative linkers to a polymer backbone through post-polymerization modification. The intro duced triazole rings serve both to anchor the stimuli-cleavable trigger groups to the polymer backbone, while also forming a functional part of the self-immolation cascade. We investigate the polymerization kinetics, post-synthetic modification, and self-immolation mechanism of a model polymer system, and discuss avenues for future studies on poly-pendant self-immolative triazoles as a modular, stimuli-responsive macromolecule platform. </p> </div> </div> </div>