文献类型：期刊文献

英文题名：Chiral Amide Chain End Directed Asymmetric Crystallization-Driven Self-Assembly of Oligo(p-phenylenevinylene) Oligomers: Influence of Structure of Amide Chain Ends

作者：Wang, Huazhang[1];Dong, Jialing[1];Zhang, Hongqing[1];Xia, Longgang[1];Du, Xinghao[1];Feng, Chun[1]

机构：[1]East China Univ Sci & Technol, Sch Mat Sci & Engn, Shanghai Key Lab Adv Polymer Mat, 130 Meilong Rd, Shanghai 200237, Peoples R China

年份：2026

外文期刊名：CHINESE JOURNAL OF CHEMISTRY

收录：;Scopus(收录号：2-s2.0-105044734030);WOS:【SCI-EXPANDED(收录号:WOS:001821688400001)】；

基金：The authors are thankful for financial supports from the National Key Research & Development Program of China (2024YFA1210700) and the National Natural Science Foundation of China (U22A20131 and 52361165657). The authors thank Dr. Kun Cui for his assistance in TEM measurements.

语种：英文

外文关键词：Asymmetric crystallization-driven self-assembly; Chain end effect; Helical nanostructure; pi-Conjugated block copolymer; Cotton effect

摘要：Asymmetric crystallization-driven self-assembly (CDSA) of pi-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 (OPV5) derivatives with comparable compositions but varying chain end structures, including OPV5-(R,R)-NH2 and OPV5-(S,S)-NH2 with a chiral amide chain end, OPV5-(1R,2S)-NH2 with a mesomeric amide chain end, and OPV5-L-NH2 with an achiral linear amide chain end, respectively, were synthesized. OPV5-(R,R)-NH2 and OPV5-(S,S)-NH2 gave helical ribbon-like micelles with a preferred handedness, whereas OPV5-(1R,2S)-NH2 and OPV5-L-NH2 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 OPV5-(R,R)-NH2 or OPV5-(S,S)-NH2 to give helical ribbon-like micelles with enhanced Cotton effect, which was dependent on both the content and structure of SO3H-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 pi-conjugated chiroptical nanostructures.