Activation and Deactivation of Chirality Transfer in the Superbundles of Sequence‐defined Stereoisomers

Discrete oligomers can be used to precisely evaluate the structure-property relationship and enable unique chiroptical activities, however, the role of stereochemical sequences on chirality transfer is still unclear. Herein, we report the successful synthesis of a series of sequence-defined chiral azobenzene (Azo) oligomers via iterative stepwise chain growth strategy. Sequence-defined stereoisomers with one single chiral (L or D) stereocenter at the α-position, ω-position and middle- (m-) position have completely different self-assembly dynamics. ω-positional stereocenter can effectively command all Azo building blocks to adopt a tilted π-π stacking along the helical superbundles, exhibiting the activation of chirality transfer. However, discrete oligomers with the stereocenter at other positions can only self-assemble into non-helical nanowires, accompanied by the deactivation of chirality transfer.Cooperative supramolecular interactions, including the π-π interaction between Azo units, the intermolecular hydrogen bonding and steric hindrance, are intrinsic driving forces for these differentiations.