Supramolecular polymerization through kinetic pathway control and living chain growth

Supramolecular polymers exhibit fascinating structures, and their properties, and thus applications, depend both on the strength and dynamics of the non-covalent bonds and on the functional properties of the monomeric building blocks. In this Review, we highlight the progress in methods developed to control supramolecular polymerization based on physicochemical insights into the thermodynamics and kinetics of non-covalent interactions. Prerequisites for polymer formation and stability, such as high binding strength (thermodynamics) between complementary receptor units, are briefly discussed, while the main focus is on the kinetic control of pathway selectivity, which in recent years has allowed seed-induced living supramolecular polymerization, chain growth-type supramolecular polymerization and the preparation of specific supramolecular polymer polymorphs and supramolecular block copolymers. Beginning with a historical retrospective, this Review highlights the progress from thermodynamically and kinetically controlled self-assembly processes towards seed-induced living supramolecular polymerization, which allows the formation of highly ordered, functional materials such as supramolecular block copolymers.