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, Ag213(C≡CR1)965- and Ag429Cl24(C≡CR2)1505- (Ag213 and Ag429, R1 =3,4,5-F3C6H2 and R2 = 4-CF3C6H4), achieved through ligand engineering and kinetic control. Single-crystal x-ray diffraction reveals that Ag213 and Ag429 have multilayered icosahedral Ag141 |(Ag13@Ag42@Ag86) and Ag297 (Ag13@Ag42@Ag92@Ag150) cores, respectively. Notably, Ag429 with 260 valence electrons is the largest Ag0-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.
Hu et al. (Thu,) studied this question.