Chiral Amide Chain End Directed Asymmetric Crystallization‐Driven Self‐Assembly of Oligo( p ‐phenylenevinylene) Oligomers: Influence of Structure of Amide Chain Ends †

Comprehensive Summary Asymmetric crystallization‐driven self‐assembly (CDSA) of π‐conjugated units has emerged as an efficient strategy to generate chiroptical nanostructures. Although the chiral chain end directed asymmetric CDSA is considered as an efficient and economical route, the reports on this subject are rare and our understanding on how the structure of chiral chain ends affects the asymmetric CDSA behavior remains limited. Herein, a series of oligo( p‐ phenylenevinylene) pentamer (OPV 5 ) derivatives with comparable compositions but varying chain end structures, including OPV 5 ‐( R , R )‐NH 2 and OPV 5 ‐( S , S )‐NH 2 with a chiral amide chain end, OPV 5 ‐(1 R ,2 S )‐NH 2 with a mesomeric amide chain end, and OPV 5 ‐L‐NH 2 with an achiral linear amide chain end, respectively, were synthesized. OPV 5 ‐( R , R )‐NH₂ and OPV 5 ‐( S , S )‐NH 2 gave helical ribbon‐like micelles with a preferred handedness, whereas OPV 5 ‐(1 R ,2 S )‐NH 2 and OPV 5 ‐L‐NH 2 afforded equal amounts of racemic isomers of helical ribbon‐like micelles. By taking advantage of electrostatic interactions, functional units of tetrakis(4‐sulfophenyl)porphyrin can co‐CDSA with OPV 5 ‐( R , R )‐NH 2 or OPV 5 ‐( S , S )‐NH 2 to give helical ribbon‐like micelles with enhanced Cotton effect, which was dependent on both the content and structure of SO 3 H‐containing species. This work not only provides some deeper insights into chiral chain end directed asymmetric CDSA behaviors, but also offers a new strategy to generate π‐conjugated chiroptical nanostructures.