Fusion growth patterns in atomically precise metal nanoclusters

Atomically precise nanoclusters of coinage metals in the 1-3 nm size regime have been intensively pursued in recent years. Such nanoclusters are attractive as they fill the gap between small molecules (<1 nm) and regular nanoparticles (>3 nm). This intermediate identity endows nanoclusters with unique physicochemical properties and provides nanochemists opportunities to understand the fundamental science of nanomaterials. Metal nanoparticles are well known to exhibit plasmon resonances upon interaction with light; however, when the particle size is downscaled to the nanocluster regime, the plasmons fade out and step-like absorption spectra characteristic of cluster sizes are manifested due to strong quantum confinement effects. Recent research has revealed that nanoclusters are commonly composed of a distinctive kernel and a surface-protecting shell (or staple-like metal-ligand motifs). Understanding the kernel configuration and evolution is one of the central topics in nanoscience research. This Review summarizes the recent progress in identifying the growth patterns of atomically precise coinage nanoclusters. Several basic kernel units have been observed, such as the M-4, M-13 and M-14 polyhedrons (where, M = metal atom). Among them, the tetrahedral M-4 and icosahedral M-13 units are the most common ones, which are adopted as building blocks to construct larger kernel structures via various fusion or aggregation modes, including the vertex- and face-sharing mode, the double-strand and alternate single-strand growth, and cyclic fusion of units, as well as the fcc-based cubic growth pattern. The identification of the kernel growth pathways has led to deeper understanding of the evolution of electronic structure and optic properties.