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<p>Atomically precise heterometallic nanoclusters (NCs) are endowed with considerable edges in tailoring active sites, modulating intermetallic synergies, and engineering electronic structures. Herein, we report an unprecedented 55-nuclearity metal NC, [Au<sub>31</sub>Cu<sub>24</sub>O<sub>2</sub>(dppy)<sub>12</sub>Cl<sub>18</sub>]<sup>3+</sup> (<b>Au</b><sub><b>31</b></sub><b>Cu</b><sub><b>24</b></sub>, dppy = 2-(diphenylphosphino)pyridine), featuring an unusual Au<sub>19</sub>@Au<sub>12</sub>Cu<sub>24</sub> core-shell architecture. The 24 Cu atoms reside exclusively within the Au-Cu alloy shell, stabilized by chlorides and pyridyl-N donors, creating a unique surface-Cu-rich configuration. The existence of interstitial oxygen atoms is crucial for the formation of the title cluster; otherwise, the smaller-sized <b>Au</b><sub><b>13−</b><Emphasis Type="BoldItalic">n</Emphasis></sub><b>Cu</b><sub><b>2+</b><Emphasis Type="BoldItalic">n</Emphasis></sub> (<i>n</i> = 0–4) NC is obtained. <b>Au</b><sub><b>31</b></sub><b>Cu</b><sub><b>24</b></sub> has achieved efficient activation of three-component cascade reactions toward polysubstituted furan synthesis, which is closely related to its surface-Cu and Au-Cu alloy shell. Notably, <b>Au</b><sub><b>31</b></sub><b>Cu</b><sub><b>24</b></sub> demonstrates high catalytic efficiency in the cascade reaction, mild reaction conditions, a broad substrate scope, as well as catalyst recyclability. These findings provide critical insights into designing synergistic heterometallic catalysts for cascade reactions and advancing the synthesis of customized alloy nanomaterials.</p>

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A novel surface-Cu-rich Au31Cu24 nanocluster for catalyzing one-pot three-component cascade synthesis of polysubstituted furans

  • 期刊论文

  • 发表日期：

    2026年3月24日

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  • Yu-Quan Qi,
  • Jian-Hua Jia,
  • Ming-Liang Tong

摘要

Atomically precise heterometallic nanoclusters (NCs) are endowed with considerable edges in tailoring active sites, modulating intermetallic synergies, and engineering electronic structures. Herein, we report an unprecedented 55-nuclearity metal NC, [Au31Cu24O2(dppy)12Cl18]3+ (Au31Cu24, dppy = 2-(diphenylphosphino)pyridine), featuring an unusual Au19@Au12Cu24 core-shell architecture. The 24 Cu atoms reside exclusively within the Au-Cu alloy shell, stabilized by chlorides and pyridyl-N donors, creating a unique surface-Cu-rich configuration. The existence of interstitial oxygen atoms is crucial for the formation of the title cluster; otherwise, the smaller-sized Au13−nCu2+n (n = 0–4) NC is obtained. Au31Cu24 has achieved efficient activation of three-component cascade reactions toward polysubstituted furan synthesis, which is closely related to its surface-Cu and Au-Cu alloy shell. Notably, Au31Cu24 demonstrates high catalytic efficiency in the cascade reaction, mild reaction conditions, a broad substrate scope, as well as catalyst recyclability. These findings provide critical insights into designing synergistic heterometallic catalysts for cascade reactions and advancing the synthesis of customized alloy nanomaterials.