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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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Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters
Abstract Chirality is ubiquitous in nature and occurs at all length scales. The development of applications for chiral nanostructures is rising rapidly. With the recent achievements of atomically precise nanochemistry, total structures of ligand‐protected Au and other metal nanoclusters (NCs) are successfully obtained, and the origins of chirality are discovered to be associated with different parts of the cluster, including the surface ligands (e.g., swirl patterns), the organic–inorganic interface (e.g., helical stripes), and the kernel. Herein, a unified picture of metal–ligand surface bonding‐induced chirality for the nanoclusters is proposed. The different bonding modes of M–X (where M = metal and X = the binding atom of ligand) lead to different surface structures on nanoclusters, which in turn give rise to various characteristic features of chirality. A comparison of Au–thiolate NCs with Au–phosphine ones further reveals the important roles of surface bonding. Compared to the Au–thiolate NCs, the Ag/Cu/Cd–thiolate systems exhibit different coordination modes between the metal and the thiolate. Other than thiolate and phosphine ligands, alkynyls are also briefly discussed. Several methods of obtaining chiroptically active nanoclusters are introduced, such as enantioseparation by high‐performance liquid chromatography and enantioselective synthesis. Future perspectives on chiral NCs are also proposed.
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- Award ID(s):
- 1808675
- PAR ID:
- 10455371
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Materials
- Volume:
- 32
- Issue:
- 41
- ISSN:
- 0935-9648
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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