Fu Kuo, Zhao Yanli, Liu Guofeng
School of Chemical Science and Engineering, Advanced Research Institute, Shanghai Key Laboratory of Chemical Assessment and Sustainability, Tongji University, Shanghai, 200092, P. R. China.
School of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371, Singapore.
Nat Commun. 2024 Nov 6;15(1):9571. doi: 10.1038/s41467-024-53928-5.
It remains challenging to elucidate the fundamental mechanisms behind the dynamic chirality inversion of supramolecular assemblies with pathway complexity. Herein, metal coordination driven assembly systems based on pyridyl-conjugated cholesterol (PVPCC) and metal ions (Ag or Al) are established to demonstrate pathway-directed, recyclable chirality inversion and assembly polymorphism. In the Ag(I)/PVPCC system, a competitive pathway leads Ag-Complex to form either kinetically controlled supramolecular polymer (Ag-SP I) or thermodynamically favored Ag-SP II, accompanied by reversible chiroptical inversion. Conversely, the Al(III)/PVPCC system displays a solvent-assisted consecutive pathway: the Al-Complex initially forms ethanol-containing Al-SP II, and subsequently converts into ethanol-free Al-SP I with opposite chiroptical performance upon thermal treatment. Moreover, stable chirality inversion in the solid state enables potential dynamic circularly polarized luminescence encryption when Ag(I)/PVPCC is co-assembled with thioflavin T. These findings provide the guidance for the dynamic modulation of chirality functionality in supramolecular materials for applications in information processing, data encryption, and chiral spintronics.
阐明具有复杂路径的超分子组装体动态手性反转背后的基本机制仍然具有挑战性。在此，基于吡啶基共轭胆固醇（PVPCC）和金属离子（Ag或Al）建立了金属配位驱动的组装体系，以证明路径导向、可回收的手性反转和组装多态性。在Ag（I）/PVPCC体系中，一条竞争路径导致Ag配合物形成动力学控制的超分子聚合物（Ag-SP I）或热力学有利的Ag-SP II，同时伴有可逆的手性光学反转。相反，Al（III）/PVPCC体系表现出溶剂辅助的连续路径：Al配合物最初形成含乙醇的Al-SP II，随后在热处理时转化为具有相反手性光学性能的无乙醇Al-SP I。此外，当Ag（I）/PVPCC与硫黄素T共组装时，固态下稳定的手性反转实现了潜在的动态圆偏振发光加密。这些发现为超分子材料中手性功能的动态调制提供了指导，可应用于信息处理、数据加密和手性自旋电子学。
