Chen Shuai-Peng, Zhang Jiajia, Cai Qi-Xiang, Si Yubing, Yuan Ying-Xue, Zang Shuang-Quan
Henan Key Laboratory of Crystalline Molecular Functional Materials, and College of Chemistry, Zhengzhou University, Zhengzhou 450001, China.
Sci Adv. 2025 Jul 18;11(29):eadx9526. doi: 10.1126/sciadv.adx9526. Epub 2025 Jul 16.
Construction of artificial microscale helical superstructures holds great significance for understanding hierarchical evolution of chiral architectures in nature. However, fabricating microscale helical superstructures from metal clusters remains mysterious and challenging. Here, we achieved hierarchically assembled helical bowties with micrometer scale via electrostatic interaction-driven co-assembly of chiral Au clusters and -1,4-cyclohexanediamine. The size and conformation matching of chiral Au and -1,4-cyclohexanediamine compared to the other amines promotes continuous chirality transfer from Au to nanoplatelets and finally to helical microbowties that follows Au molecular chirality. We elucidated hierarchical evolution mechanism of morphology from nanoplatelets to microcake and to helical microbowties through gradual helical stacking and twisting of nanoplatelets. Furthermore, these helical microbowties exhibited excellent switchable photoluminescence and circularly polarized luminescence characteristics governed by dissociation and recombination of electrostatic interactions. This work demonstrates the formation of controllable metal cluster-based helical microbowties and deepens the understanding of chirality transfer and expression at microscale.
构建人工微尺度螺旋超结构对于理解自然界中手性结构的层级演化具有重要意义。然而，利用金属簇制备微尺度螺旋超结构仍然充满神秘且具有挑战性。在此，我们通过手性金簇与1,4 - 环己二胺的静电相互作用驱动共组装，实现了微米级的分层组装螺旋领结结构。与其他胺类相比，手性金和1,4 - 环己二胺的尺寸和构象匹配促进了手性从金到纳米片再到螺旋微领结的连续传递，该螺旋微领结遵循金分子的手性。我们通过纳米片的逐渐螺旋堆积和扭曲，阐明了从纳米片到微饼再到螺旋微领结的形态层级演化机制。此外，这些螺旋微领结表现出由静电相互作用的解离和重组控制的优异可切换光致发光和圆偏振发光特性。这项工作展示了可控的基于金属簇的螺旋微领结的形成，并加深了对微尺度上手性传递和表达的理解。
