Synthesis and dynamic covalent assembly of rim-differentiated dithiol-substituted pillar[5]arene positional isomers.

We report the synthesis of two rim-differentiated pillar[5]arene dithiol isomers: the adjacent (A1/B1) and non-adjacent (A1/C1) derivatives. These two isomers lead to completely divergent disulfide-based dynamic covalent library outcomes. While the adjacent macrocycle affords cyclic dimers and trimers, including homochiral and heterochiral stereoisomers, the non-adjacent counterpart yields higher-order oligomers and polymers.