Dynamic Control over Hierarchically Dendritic Architectures of Simple Heterogenous Monomers by Living Supramolecular Assembly.

The successful preparation of supramolecular block copolymers (SBCPs) by living supramolecular assembly technology requires two kinetic systems in which both the seed (nucleus) and heterogenous monomer providers are in non-equilibrium. However, employing simple monomers to construct the SBCPs via this technology is almost impossible because the low spontaneous nucleation barrier of simple molecules prevents the formation of kinetic states. Here, with the help of confinement from layered double hydroxide (LDH), various simple monomers successfully form living supramolecular co-assemblies (LSCA). LDH overcomes a considerable energy barrier to obtain living seeds to support the growth of the inactivated second monomer. The ordered LDH topology is sequentially mapped to the seed, second monomer, and binding sites. Thus, the multidirectional binding sites are endowed with the ability to branch, making the branch length of dendritic LSCA reach its maximum value of 3.5 cm so far. The strategy of universality will guide exploration into the development of multi-function and multi-topology advanced supramolecular co-assemblies.