Cheng Caikun, Li Benyou, Feng Zhenyu, Liu Rongjuan, Bi Yuting, Li Qiang, Wei Jingjing, Yang Zhijie
Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, P. R. China.
J Am Chem Soc. 2025 Jan 15;147(2):1803-1812. doi: 10.1021/jacs.4c13831. Epub 2025 Jan 7.
Chirality epitomizes the sophistication of chemistry, representing some of its most remarkable achievements. Yet, the precise synthesis of chiral structures from achiral building blocks remains a profound and enduring challenge in synthetic chemistry and materials science. Here, we demonstrate that achiral colloidal nanocrystals, including Au and Ag nanocrystals, can assemble into long-range-ordered helical assemblies with the assistance of chiral molecules. The synchronized aggregation kinetics between colloidal silver or gold nanocrystals and π-conjugated perylene diimide molecules enables the nanocrystals to precisely follow the helical pathways of the molecular assemblies. This results in the formation of helical nanocrystal assemblies extending over tens of micrometers. These helically organized nanocrystals, exhibiting high positional precision, display linear size-dependent chiroptical properties. Furthermore, more intricate helical assemblies, featuring triple, quadruple, and quintuple nanocrystal strands, can be observed in addition to the commonly encountered double helical assemblies. Finally, these helical assemblies, composed of discrete Ag nanocrystals, can fuse into continuous AgS helical structures following a sulfidation reaction, ultimately leading to the formation of diverse metal sulfide helices through cation exchange processes.
手性体现了化学的精妙之处，代表了其一些最卓越的成就。然而，从非手性构建块精确合成手性结构在合成化学和材料科学中仍然是一个深刻且持久的挑战。在此，我们证明包括金和银纳米晶体在内的非手性胶体纳米晶体能够在手性分子的辅助下组装成长程有序的螺旋组装体。胶体银或金纳米晶体与π共轭苝二酰亚胺分子之间同步的聚集动力学使纳米晶体能够精确地沿着分子组装体的螺旋路径排列。这导致形成了延伸数十微米的螺旋纳米晶体组装体。这些螺旋组织的纳米晶体具有高位置精度，展现出与线性尺寸相关的手性光学性质。此外，除了常见的双螺旋组装体之外，还能观察到更复杂的螺旋组装体，其具有三股、四股和五股纳米晶体链。最后，这些由离散银纳米晶体组成的螺旋组装体在硫化反应后可以融合成连续的AgS螺旋结构，最终通过阳离子交换过程形成各种金属硫化物螺旋体。
