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功能性手性纳米组装体中的多面体低聚倍半硅氧烷

Polyhedral Oligosilsesquioxanes in Functional Chiral Nanoassemblies.

作者信息

An Shuguo, Hao Aiyou, Xing Pengyao

机构信息

School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, P. R. China.

出版信息

Angew Chem Int Ed Engl. 2021 Apr 26;60(18):9902-9912. doi: 10.1002/anie.202100044. Epub 2021 Mar 18.

DOI:10.1002/anie.202100044
PMID:33529451
Abstract

Incorporation of giant molecular nanoparticles with atomic precision into chiral nanoassemblies facilitates the fabrication of functional ordered phases with supramolecular chirality, which remains mysterious. Reported here is the first example of polyhedral oligosilsesquioxane (POSS) derivatives that self-assemble into well-defined chiral nanoassemblies. POSSs were covalently conjugated to N-terminal aromatic amino acids, which self-assembled into nanohelices and twists with explicit handedness tuned by solvent polarity. Chiral nanoassemblies showed active chiroptical responses including Cotton effects and circularly polarized luminescence. The chiral systems can bind guest molecules by charge-transfer interactions, whereby self-assembled structures, chiroptical activities, and luminescent colors were further modulated. The unique coassembly systems were applied for instant information encryption and storage with multiple luminescent displays. This work offers a new protocol for the design of functional chiral materials of POSS by molecular self-assembly.

摘要

将具有原子精度的巨型分子纳米颗粒纳入手性纳米组装体中,有助于制造具有超分子手性的功能性有序相,这仍然是个谜。本文报道了首例自组装成明确手性纳米组装体的多面体低聚倍半硅氧烷(POSS)衍生物。POSS与N端芳香族氨基酸共价共轭,这些氨基酸自组装成纳米螺旋和扭曲结构,其手性由溶剂极性明确调节。手性纳米组装体表现出包括科顿效应和圆偏振发光在内的活性手性光学响应。手性体系可通过电荷转移相互作用结合客体分子,从而进一步调节自组装结构、手性光学活性和发光颜色。独特的共组装体系被应用于具有多种发光显示的即时信息加密和存储。这项工作为通过分子自组装设计功能性POSS手性材料提供了一种新方案。

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