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An Atomically Precise Pyrazolate-Protected Copper Nanocluster Exhibiting Exceptional Stability and Catalytic

Yu-Mei Wang1, Xiao-Chun Lin1, Kai-Ming Mo1

  • 1Department College of Chemistry and Materials Science, Guangdong Provincial Key Laboratory of Functional Supramolecular Coordination Materials and Applications Jinan University, Guangzhou, Guangdong 510632, P. R. China.

Angewandte Chemie (International Ed. in English)
|December 27, 2022
PubMed
Summary

Atomically precise copper nanoclusters (Cu-NCs) are challenging to synthesize stably. This study introduces a pyrazolate-protected Cu-NC (Cu8) with exceptional stability in various conditions and effective catalytic activity.

Keywords:
CatalysisCopper NanoclusterIndolizinesLigand TransformationPyrazolate

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Area of Science:

  • Materials Science
  • Nanotechnology
  • Catalysis

Background:

  • Synthesizing atomically precise copper nanoclusters (Cu-NCs) with high chemical stability is crucial for their practical applications.
  • Existing methods often yield Cu-NCs with limited stability, hindering their use in demanding environments.

Purpose of the Study:

  • To develop a highly stable pyrazolate-protected copper nanocluster (Cu8).
  • To investigate the chemical stability of Cu8 in various harsh conditions (solid-state and solution).
  • To evaluate the catalytic performance of Cu8 in organic synthesis.

Main Methods:

  • Synthesis of pyrazolate-protected copper nanoclusters (Cu8).
  • Chemical stability tests involving boiling water, hydrogen peroxide, concentrated acid (HCl), and saturated base (KOH).
  • Solution stability analysis using oxygen, organic acid (HOAc), and base (dibutylamine) with 1H NMR and UV/Vis spectroscopy.
  • Catalytic activity assessment for indolizine synthesis and reusability tests.

Main Results:

  • The synthesized Cu8 exhibited exceptional chemical stability, remaining intact after exposure to boiling water, H2O2, 1 M HCl, and ~20 M KOH.
  • In solution, Cu8 maintained its structural integrity against oxygen, 100 eq. HOAc, and 400 eq. dibutylamine.
  • Cu8 demonstrated excellent catalytic activity for indolizine synthesis and could be reused for at least 10 cycles without performance loss.

Conclusions:

  • The pyrazolate-protected Cu8 represents a significant advancement in the development of chemically stable copper nanoclusters.
  • Its robust stability and catalytic efficiency make it a promising candidate for various chemical transformations, particularly in alkaline media.