Atomically precise gold nanoclusters with diameters of 1–3 nm have attracted considerable research interests in the past decade because they fill the gap between small organic‐metal complexes (<1 nm) and metal nanoparticles (>3 nm). Au13 nanocluster with icosahedral structure is a ubiquitous unit widely applied in nanocluster assembly. In this minireview, we introduce the optical properties of gold nanoclusters constructed from Au13 units. We first discuss the optical absorption and photoluminescence of Au13, Au25, Au37, and Au60 clusters. We then discuss the ultrafast dynamics, the detailed excited‐state deactivation processes, and the origin of coherent oscillations of the Au13 homologous clusters. Finally, we provide our outlook on the future direction on this topic.

Coherent vibrational dynamics can be observed in atomically precise gold nanoclusters using femtosecond time-resolved pump-probe spectroscopy. It can not only reveal the coupling between electrons and vibrations, but also reflect the mechanical and electronic properties of metal nanoclusters, which holds potential applications in biological sensing and mass detection. Here, we investigated the coherent vibrational dynamics of [Au25(SR)18]− nanoclusters by ultrafast spectroscopy and revealed the origins of these coherent vibrations by analyzing their frequency, phase and probe wavelength distributions. Strong coherent oscillations with frequency of 40 cm−1 and 80 cm−1 can be reproduced in the excited state dynamics of [Au25(SR)18]−, which should originate from acoustic vibrations of the Au13 metal core. Phase analysis on the oscillations indicates that the 80 cm−1 mode should arise from the frequency modulation of the electronic states while the 40 cm−1 mode should originate from the amplitude modulation of the dynamic spectrum. Moreover, it is found that the vibration frequencies of [Au25(SR)18]− obtained in pump-probe measurements are independent of the surface ligands so that they are intrinsic properties of the metal core. These results are of great value to understand the electron-vibration coupling of metal nanoclusters.

A single electron can have a significant influence on the excited state dynamics of rod-shaped Au25 nanoclusters.