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Tertiary Chiral Nanostructures from C−H⋅⋅⋅F Directed Assembly of Chiroptical Superatoms
Author(s) -
Shen Hui,
Xu Zhen,
Wang Lingzheng,
Han YingZi,
Liu Xianhu,
Malola Sami,
Teo Boon K.,
Häkkinen Hannu,
Zheng Nanfeng
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202108141
Subject(s) - nanoclusters , superatom , chirality (physics) , chemistry , enantiomer , metal , nanostructure , crystallography , nanotechnology , stereochemistry , materials science , computational chemistry , density functional theory , organic chemistry , physics , chiral symmetry breaking , quantum mechanics , nambu–jona lasinio model , quark
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.