Revealing the chirality origin and homochirality crystallization of Ag14 nanocluster at the molecular level

Xiao-Qian Liang, Ying-Zhou Li, Zhi Wang, Shan-Shan Zhang, Yi-Cheng Liu, Zhao-Zhen Cao, Lei Feng, Zhi-Yong Gao, Qing-Wang Xue, Chen-Ho Tung and Di Sun ()
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Xiao-Qian Liang: Shandong University
Ying-Zhou Li: Qilu University of Technology (Shandong Academy of Science)
Zhi Wang: Shandong University
Shan-Shan Zhang: Shandong University
Yi-Cheng Liu: Shandong University
Zhao-Zhen Cao: Shandong University
Lei Feng: Shandong University
Zhi-Yong Gao: Henan Normal University
Qing-Wang Xue: Liaocheng University
Chen-Ho Tung: Shandong University
Di Sun: Shandong University

Nature Communications, 2021, vol. 12, issue 1, 1-10

Abstract: Abstract Although chirality is an ever-present characteristic in biology and some artificial molecules, controlling the chirality and demystifying the chirality origin of complex assemblies remain challenging. Herein, we report two homochiral Ag14 nanoclusters with inherent chirality originated from identical rotation of six square faces on a Ag8 cube driven by intra-cluster π···π stacking interaction between pntp− (Hpntp = p-nitrothiophenol) ligands. The spontaneous resolution of the racemic (SD/rac-Ag14a) to homochiral nanoclusters (SD/L-Ag14 and SD/R-Ag14) can be realized by re-crystallizing SD/rac-Ag14a in acetonitrile, which promotes the homochiral crystallization in solid state by forming C–H···O/N hydrogen bonds with nitro oxygen atoms in pntp− or aromatic hydrogen atoms in dpph (dpph = 1,6-bis(diphenylphosphino)hexane) on Ag14 nanocluster. This work not only provides strategic guidance for the syntheses of chiral silver nanoclusters in an all-achiral environment, but also deciphers the origin of chirality at molecular level by identifying the special effects of intra- and inter-cluster supramolecular interactions.

Date: 2021
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DOI: 10.1038/s41467-021-25275-2

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