Chiral inheritance effect in the reactive cystine-based coassembly system

Controlled chemical reactions in the condensed state are key steps in designing smart materials. Due to the absence of diffusion and sufficient molecular collision, the reaction efficiency in the solid or aggregated state is expectedly much lower than the solution phase. Herein we report the templating effects in self-assemblies undergoing multiple reactions using an aromatic cystine derivative. Disulfide bond cleavage into cysteine triggered by a reductant is quantitative in aggregates, leading to the molecular rearrangement. Coassembled with a guest pentafluoropyridine through π-hole/π interaction allows for a cascade two-step reaction including reduction and aromatic nucleophilic substitution. These reactions in the condensed, self-assembled state are efficient with significant impacts on the structures of nanoarchitectures. Interestingly, the chiral expression at macroscopic scale and corresponding chiroptical activities exhibit templating and inheritance effect thanks to the sacrificial templating role of pristine aggregates. We introduce new type efficient reactions in the self-assembled states, realizing flexible control by introducing guest, and unveil the chiral inheritance effect in topochemical evolutions. Controlled reactions in solid or self-assembled states underpin dynamic materials and topochemical processes but suffer reduced efficiency without diffusion. Here, the authors report that an aromatic cystine derivative undergoes multiple topochemical steps with strong templating and chiral inheritance.