Tertiary Chiral Nanostructures from C−H⋅⋅⋅F Directed Assembly of Chiroptical Superatoms
Hui Shen, Zhen Xu, Lingzheng Wang, Ying‐Zi Han, Xianhu Liu, Sami Malola, Boon K. Teo, Hannu Häkkinen, Nanfeng Zheng
Abstract
Abstract We report the synthesis and structure of tertiary chiral nanostructures with 100 % optical purity. A novel synthetic strategy, using chiral reducing agent, R and S‐BINAPCuBH 4 (BINAP is 2,2′‐Bis(diphenylphosphino)‐1,1′‐binaphthyl), is developed to access to atomically precise, intrinsically chiral [Au 7 Ag 6 Cu 2 (R‐ or S‐BINAP) 3 (SCH 2 Ph) 6 ]SbF 6 nanoclusters in one‐pot synthesis. The clusters represent the first tri‐metallic superatoms with inherent chirality and fair stability. Both metal distribution (primary) and ligand arrangement (secondary) of the enantiomers exhibited perfect mirror images, and unprecedentedly, the self‐assembly driven by the C−H⋅⋅⋅F interaction between the phenyl groups of the superatom moieties and SbF 6 − anions induced the formation of bio‐mimic left‐ and right‐handed helices, achieving the tertiary chiral nanostructures. DFT calculations revealed the connections between the molecular details and chiral optical activity.