Tertiary Chiral Nanostructures from C‐H∙∙∙F Directed Assembly of Chiroptical Superatoms
Shen, H., Xu, Z., Wang, L., Han, Y.-Z., Liu, X., Malola, S., Teo, B. K., Häkkinen, H., & Zheng, N. (2021). Tertiary Chiral Nanostructures from C‐H∙∙∙F Directed Assembly of Chiroptical Superatoms. Angewandte Chemie, 60(41), 22411-22416. https://doi.org/10.1002/anie.202108141
Published inAngewandte Chemie
Xu, Zhen |
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Chiral hierarchical structures are universal in nature, whereas quite challenging to mimic in man-made synthesis. We report herein 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. Density functional theory calculations revealed the connections between the molecular details and chiral optical activity. ...
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Related funder(s)Academy of Finland
Funding program(s)Academy Programme, AoF; Research post as Academy Professor, AoF; Research costs of Academy Professor, AoF
Additional information about fundingWe thank the National Key R&D Program of China (2017YFA0207302), the NNSF of China (21890752, 21731005, 21420102001, 21721001) and the 111 Project (B08027) for financial support. The computational work in the University of Jyväskylä was supported by the Academy of Finland through grants 292352, 315549, 319208. HH acknowledges support from China's National Innovation and Intelligence Introduction Base visitor program. The computations were made at the CSC supercomputing center in Finland. ...
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