Small symmetry-breaking triggering large chiroptical responses of Ag70 nanoclusters

Xi-Ming Luo, Chun-Hua Gong, Fangfang Pan, Yubing Si, Jia-Wang Yuan, Muhammad Asad, Xi-Yan Dong (), Shuang-Quan Zang () and Thomas C. W. Mak
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Xi-Ming Luo: Zhengzhou University
Chun-Hua Gong: Zhengzhou University
Fangfang Pan: College of Chemistry Central China Normal University
Yubing Si: Zhengzhou University
Jia-Wang Yuan: Zhengzhou University
Muhammad Asad: Zhengzhou University
Xi-Yan Dong: Zhengzhou University
Shuang-Quan Zang: Zhengzhou University
Thomas C. W. Mak: Zhengzhou University

Nature Communications, 2022, vol. 13, issue 1, 1-8

Abstract: Abstract The origins of the chiroptical activities of inorganic nanostructures have perplexed scientists, and deracemization of high-nuclearity metal nanoclusters (NCs) remains challenging. Here, we report a single-crystal structure of Rac-Ag70 that contains enantiomeric pairs of 70-nuclearity silver clusters with 20 free valence electrons (Ag70), and each of these clusters is a doubly truncated tetrahedron with pseudo-T symmetry. A deracemization method using a chiral metal precursor not only stabilizes Ag70 in solution but also enables monitoring of the gradual enlargement of the electronic circular dichroism (CD) responses and anisotropy factor gabs. The chiral crystals of R/S-Ag70 in space group P21 containing a pseudo-T-symmetric enantiomeric NC show significant kernel-based and shell-based CD responses. The small symmetry breaking of Td symmetry arising from local distortion of Ag−S motifs and rotation of the apical Ag3 trigons results in large chiroptical responses. This work opens an avenue to construct chiral medium/large-sized NCs and nanoparticles, which are promising for asymmetric catalysis, nonlinear optics, chiral sensing, and biomedicine.

Date: 2022
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DOI: 10.1038/s41467-022-28893-6

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