Self-Assembly Can Direct Dynamic Covalent Bond Formation Towards Diversity or Specificity

With the advent of reversible covalent chemistry the study of the interplay between covalent bond formation and non-covalent interactions has become increasingly relevant. Here we report that the interplay between reversible disulfide chemistry and self-assembly can give rise either to molecular diversity, i.e. the emergence of a unprecedentedly large range of macrocycles or to molecular specificity, i.e. the autocatalytic emergence of a single species. The two phenomena are the result of two different modes of self-assembly, demonstrating that control over self-assembly pathways can enable control over covalent bond formation.