文献类型：期刊文献

英文题名：Chiral Bisammonium-Directed Living Crystallization-Driven Self-Assembly Toward the Preparation of Nanostructures with Controlled Dimensions and Tunable Chiroptical Properties

作者：Xiang, Bo[1];Wu, Hongluo[1];Xia, Longgang[3];Huang, Xiaoyu[1,2];Lu, Guolin[1];Feng, Chun[1,3]

机构：[1]Univ Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Fluorine & Nitrogen Chem & Adv Mat, Shanghai 200032, Peoples R China;[2]Macau Univ Sci & Technol, Fac Med, Macau 999078, Peoples R China;[3]East China Univ Sci & Technol, Sch Mat Sci & Engn, Shanghai Key Lab Adv Polymer Mat, Shanghai 200237, Peoples R China

年份：2025

卷号：58

期号：23

起止页码：12489

外文期刊名：MACROMOLECULES

收录：;EI(收录号：20255119755063);WOS:【SCI-EXPANDED(收录号:WOS:001618645900001)】；

基金：The authors are thankful for financial support from the National Key Research & Development Program of China (2024YFA1210700), the National Natural Science Foundation of China (U22A20131 and 52361165657), and the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB0590000). The authors thank Dr. Kun Cui for his assistance with TEM measurements and beamline BL16B1 at SSRF for providing the beam time.

语种：英文

外文关键词：Bridges - Chains - Chirality - Circular polarization - Cryptography - Dichroism - Ethers - Fabrication - Luminescence - Morphology - Nanostructures - Rigid structures - Self assembly

摘要：Polymer nanostructures with controlled morphology and tunable chiroptical activities of circular dichroism (CD) and circularly polarized luminescence (CPL), showing promising applications ranging from information encryption to display, have attracted growing interest. However, their facile and precise preparation remains a great challenge. In this contribution, we report a chiral bisammonium-directed crystallization-driven self-assembly strategy to generate uniform ribbon-like micelles of controlled length and tunable CD and CPL spectra. By a heating-cooling protocol, the CDSA of crown ether-terminated OPV4 and OPV5 (OPV = oligo(p-phenylenevinylene), where the subscript represents the number of repeat units) gave ribbon-like micelles with lengths up to tens of micrometers and widths up to hundreds of nanometers. The bisammonium was supposed to act as a "bridge" and form a sandwich-like complex with two crown ethers at two adjacent OPV chain ends. Owing to the chiral structure of bisammonium and the ordered packing of OPV units, chiral bisammonium with a relatively rigid conformation would induce slight twisting of OPV units, which endowed the resulting ribbon-like micelles with tunable CD and CPL properties, with a high g lum (dissymmetry factor) value up to the order of 10-2. More importantly, it was found that the chiral bisammonium can serve as a "bridge" between two adjacent crown ether chain ends of two separate OPV units to enhance the affinity of free unimers to the ends of seed micelles. This "bridge" effect not only promoted the efficiency of seeded growth to give uniform fiber-like micelles in a controlled way but also directed the packing of OPV4-18C6 to endow the resulting micelles with chiroptical properties. Since the CPL property of the resulting OPV4-18C6-based nanostructures can be regulated by the chirality of bisammoniums, proof-of-concept anticounterfeiting materials can be fabricated from the CDSA of OPV4-18C6 with different chiral bisammoniums. Given the robustness of (living) CDSA and the great variety of noncovalent interactions, the concept of noncovalent-interaction-directed CDSA can be extended to other polymer systems to create diverse nanostructures with controlled dimensions and tunable CD and CPL properties.