Autocatalytic Time-Dependent Evolution of Metastable Two-Component Supramolecular Assemblies to Self-Sorted or Coassembled State.

Despite substantial effort devoted in the history of supramolecular chemistry, synthetic supramolecular systems still lag behind biomolecular systems in terms of complexity and functionality. This is because biomolecular systems function in a multicomponent molecular network under out-of-equilibrium conditions. Here we report two-component supramolecular assemblies that are metastable and thus show time-dependent evolution. We found that the systems undergo either self-sorting or coassembly in time depending on the combination of components. Interestingly, this outcome, which had been previously achievable only under specific conditions, emerged from the two-component systems as a result of synergistic or reciprocal interplay between the coupled equilibria. We believe that this study sheds light on the similarity between synthetic and biomolecular systems and promotes better understanding of their intricate kinetic behaviors.