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<p>Copper nanoclusters with precise structures have gained increasing interest due to their lower price, excellent photophysical properties, and applications. The oxidative instability of Cu(0) clusters presents challenges for their synthesis. Moreover, ligand control of electronic states in Cu NCs and its impact on stability remain elusive. In this work, a paddle-wheel pre-construction strategy was used for the synthesis of eight benzoate-protected copper <b>Cu</b><sub><b>28</b></sub> NCs. Unexpectedly, benzoate ligands can obviously reshape the electronic landscape of <b>Cu</b><sub><b>28</b></sub>, resulting in 15 hydrides and 1–2 free electrons, which represents the discovery of BCC-structured Cu NCs with Cu(0) species. Characterization methods, including ESI-MS, XAFS, XPS, Auger spectroscopy, and DFT calculations, were carried out to determine the oxidation states of Cu and the distribution of hydrides. Notably, <b>Cu</b><sub><b>28</b></sub>-based catalysts enable efficient azide-alkyne cycloaddition under ambient conditions with TON values as high as 424.0. More importantly, <b>Cu</b><sub><b>28</b></sub> NCs exhibit outstanding stability and can be synthesized on a gram-scale with a high yield of ∼70%. Our research shows that the type of carboxylate ligands can not only fine-tune the HOMO and LUMO energy levels as previously reported but also affect the oxidation state of the inner Cu atom and the electron cloud distribution of the cluster. The paddle-wheel pre-construction strategy also provides a new approach for the large-scale preparation of copper nanocluster catalysts with precise structure and high stability for commercial applications.</p>

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A paddle-wheel pre-construction strategy towards benzoate-protected Cu28 nanoclusters with reshaped electronic landscape for the AAC click reaction

  • 期刊论文

  • 发表日期：

    2025年12月9日

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  • Mei Qu,
  • Miao-Miao Qiao,
  • Fu-Qiang Zhang,
  • Yong Lei,
  • Nan Zhang,
  • Shi-Li Li,
  • Xian-Ming Zhang

摘要

Copper nanoclusters with precise structures have gained increasing interest due to their lower price, excellent photophysical properties, and applications. The oxidative instability of Cu(0) clusters presents challenges for their synthesis. Moreover, ligand control of electronic states in Cu NCs and its impact on stability remain elusive. In this work, a paddle-wheel pre-construction strategy was used for the synthesis of eight benzoate-protected copper Cu28 NCs. Unexpectedly, benzoate ligands can obviously reshape the electronic landscape of Cu28, resulting in 15 hydrides and 1–2 free electrons, which represents the discovery of BCC-structured Cu NCs with Cu(0) species. Characterization methods, including ESI-MS, XAFS, XPS, Auger spectroscopy, and DFT calculations, were carried out to determine the oxidation states of Cu and the distribution of hydrides. Notably, Cu28-based catalysts enable efficient azide-alkyne cycloaddition under ambient conditions with TON values as high as 424.0. More importantly, Cu28 NCs exhibit outstanding stability and can be synthesized on a gram-scale with a high yield of ∼70%. Our research shows that the type of carboxylate ligands can not only fine-tune the HOMO and LUMO energy levels as previously reported but also affect the oxidation state of the inner Cu atom and the electron cloud distribution of the cluster. The paddle-wheel pre-construction strategy also provides a new approach for the large-scale preparation of copper nanocluster catalysts with precise structure and high stability for commercial applications.