Abstract With the recent establishment of atomically precise nanochemistry, capabilities toward programmable control over the nanoparticle size and structure are being developed. Advances in the synthesis of atomically precise nanoclusters (NCs, 1–3 nm) have been made in recent years, and more importantly, their total structures (core plus ligands) have been mapped out by X‐ray crystallography. These ultrasmall Au nanoparticles exhibit strong quantum‐confinement effect, manifested in their optical absorption properties. With the advantage of atomic precision, gold‐thiolate nanoclusters (Aun(SR)m) are revealed to contain an inner kernel, Au–S interface (motifs), and surface ligand (‐R) shell. Programming the atomic packing into various crystallographic structures of the metal kernel can be achieved, which plays a significant role in determining the optical properties and the energy gap (Eg) of NCs. When the size increases, a general trend is observed for NCs with fcc or decahedral kernels, whereas those NCs with icosahedral kernels deviate from the general trend by showing comparably smallerEg. Comparisons are also made to further demonstrate the more decisive role of the kernel structure over surface motifs based on isomeric Au NCs and NC series with evolving kernel or motif structures. Finally, future perspectives are discussed.
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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.
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- Award ID(s):
- 1808675
- PAR ID:
- 10172599
- Date Published:
- Journal Name:
- Nanoscale
- Volume:
- 11
- Issue:
- 41
- ISSN:
- 2040-3364
- Page Range / eLocation ID:
- 19158 to 19165
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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