Deciphering icosahedra structural evolution with atomically precise silver nanoclusters.

Hu, Feng; Yang, Gaoyuan; Zheng, Lu-Ming; Liang, Gui-Jie; Wang, Quan-Ming · Science · 2025

basic_science · Level V

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Abstract

Determining the atomic structure of nanoparticles (NPs) is critical for understanding their structural evolution and properties. However, controlling the growth of multiply-twinned metal NPs remains challenging because of numerous competing pathways. In this work, we report the synthesis of two giant silver icosahedral nanoclusters, [Ag<sub>213</sub>(C≡CR1)<sub>96</sub>]<sup>5-</sup> and [Ag<sub>429</sub>Cl<sub>24</sub>(C≡CR2)<sub>150</sub>]<sup>5-</sup> (Ag<sub>213</sub> and Ag<sub>429</sub>, R1 =3,4,5-F<sub>3</sub>C<sub>6</sub>H<sub>2</sub> and R2 = 4-CF<sub>3</sub>C<sub>6</sub>H<sub>4</sub>), achieved through ligand engineering and kinetic control. Single-crystal x-ray diffraction reveals that Ag<sub>213</sub> and Ag<sub>429</sub> have multilayered icosahedral Ag<sub>141</sub> |(Ag<sub>13</sub>@Ag<sub>42</sub>@Ag<sub>86</sub>) and Ag<sub>297</sub> (Ag<sub>13</sub>@Ag<sub>42</sub>@Ag<sub>92</sub>@Ag<sub>150</sub>) cores, respectively. Notably, Ag<sub>429</sub> with 260 valence electrons is the largest Ag<sup>0</sup>-containing nanocluster reported to date. These two giant silver nanoclusters are metallic in nature, as confirmed by their plasmonic absorption and pump-power-dependent excited-state dynamics. Their atomically precise structures support the layer-by-layer evolution from nuclei to seeds of silver icosahedra.