Adaptive Covalent Networks Enabled by Dual Reactivity: The Evolution of Reversible Covalent Bonds, Their Molecular Assemblies, and Guest Recognition

Adaptive chemistry allows transformation and selection within molecular networks, and adaptive systems composed of different types of dynamic covalent reactions (DCRs) are challenging. Herein, we demonstrate dual reactivity-based covalent networks encompassing the regulation of and switching between C–N- and C–S-based reversible covalent assemblies. The creation and exchange of C–N- or C–S-derived assemblies exhibiting diverse architectures, including linear structures, macrocycles, and cages, were achieved. The shift of reactivity then permitted the interconversion between C–N- and C–S-containing assemblies. Moreover, the adaption of intramolecular and intermolecular scaffolds was feasible via linker design. The latent hemiaminal chirality center offered a pathway for the induction of chirality within assemblies. Finally, switchable structural change and controlled extraction of ions were realized with Hg2+ as a guest for macrocycles. The remarkable complexity of networks described herein could open the door for the utility in sophisticated functional systems.