Deciphering icosahedra structural evolution with atomically precise silver nanoclusters
Feng Hu, Gaoyuan Yang, Lu-Ming Zheng, Guijie Liang, Quan‐Ming Wang
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 213 (C≡CR1) 96 ] 5− and [Ag 429 Cl 24 (C≡CR2) 150 ] 5− (Ag 213 and Ag 429 , R1 =3,4,5-F 3 C 6 H 2 and R2 = 4-CF 3 C 6 H 4 ), achieved through ligand engineering and kinetic control. Single-crystal x-ray diffraction reveals that Ag 213 and Ag 429 have multilayered icosahedral Ag 141 |(Ag 13 @Ag 42 @Ag 86 ) and Ag 297 (Ag 13 @Ag 42 @Ag 92 @Ag 150 ) cores, respectively. Notably, Ag 429 with 260 valence electrons is the largest Ag 0 -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.