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Small symmetry-breaking triggering large chiroptical responses of Ag70 nanoclusters

Author

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  • Xi-Ming Luo

    (Zhengzhou University
    Henan Polytechnic University)

  • Chun-Hua Gong

    (Zhengzhou University)

  • Fangfang Pan

    (College of Chemistry Central China Normal University)

  • Yubing Si

    (Zhengzhou University)

  • Jia-Wang Yuan

    (Zhengzhou University
    Henan Polytechnic University)

  • Muhammad Asad

    (Zhengzhou University)

  • Xi-Yan Dong

    (Zhengzhou University
    Henan Polytechnic University)

  • Shuang-Quan Zang

    (Zhengzhou University)

  • Thomas C. W. Mak

    (Zhengzhou University
    The Chinese University of Hong Kong, Shatin)

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.

Suggested Citation

  • Xi-Ming Luo & Chun-Hua Gong & Fangfang Pan & Yubing Si & Jia-Wang Yuan & Muhammad Asad & Xi-Yan Dong & Shuang-Quan Zang & Thomas C. W. Mak, 2022. "Small symmetry-breaking triggering large chiroptical responses of Ag70 nanoclusters," Nature Communications, Nature, vol. 13(1), pages 1-8, December.
  • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-28893-6
    DOI: 10.1038/s41467-022-28893-6
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    References listed on IDEAS

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    1. Juanzhu Yan & Sami Malola & Chengyi Hu & Jian Peng & Birger Dittrich & Boon K. Teo & Hannu Häkkinen & Lansun Zheng & Nanfeng Zheng, 2018. "Co-crystallization of atomically precise metal nanoparticles driven by magic atomic and electronic shells," Nature Communications, Nature, vol. 9(1), pages 1-8, December.
    2. 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 & Di Sun, 2021. "Revealing the chirality origin and homochirality crystallization of Ag14 nanocluster at the molecular level," Nature Communications, Nature, vol. 12(1), pages 1-10, December.
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    Cited by:

    1. Li-Juan Liu & Fahri Alkan & Shengli Zhuang & Dongyi Liu & Tehseen Nawaz & Jun Guo & Xiaozhou Luo & Jian He, 2023. "Atomically precise gold nanoclusters at the molecular-to-metallic transition with intrinsic chirality from surface layers," Nature Communications, Nature, vol. 14(1), pages 1-12, December.
    2. Xue-Jing Zhai & Meng-Yu Luo & Xi-Ming Luo & Xi-Yan Dong & Yubing Si & Chong Zhang & Zhen Han & Runping Han & Shuang-Quan Zang & Thomas C. W. Mak, 2024. "Hierarchical assembly of Ag40 nanowheel ranging from building blocks to diverse superstructure regulation," Nature Communications, Nature, vol. 15(1), pages 1-11, December.

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