Ligand Design in Ligand-Protected Gold Nanoclusters.

The design of surface ligands is crucial for ligand-protected gold nanoclusters (Au NCs). Besides providing good protection for Au NCs, the surface ligands also play the following two important roles: i) as the outermost layer of Au NCs, the ligands will directly interact with the exterior environment (e.g., solvents, molecules and cells) influencing Au NCs in various applications; and ii) the interfacial chemistry between ligands and gold atoms can determine the structures, as well as the physical and chemical properties of Au NCs. A delicate ligand design in Au NCs (or other metal NCs) needs to consider the covalent bonds between ligands and gold atoms (e.g., gold-sulfur (Au-S) and gold-phosphorus (Au-P) bond), the physics forces between ligands (e.g., hydrophobic and van der Waals forces), and the ionic forces between the functional groups of ligands (e.g., carboxylic (COOH) and amine group (NH2 )); which form the underlying chemistry and discussion focus of this review article. Here, detailed discussions on the effects of surface ligands (e.g., thiolate, phosphine, and alkynyl ligands; or hydrophobic and hydrophilic ligands) on the synthesis, structures, and properties of Au NCs; highlighting the design principles in the surface engineering of Au NCs for diverse emerging applications, are provided.

Unraveling the Impact of Gold(I)-Thiolate Motifs on the Aggregation-Induced Emission of Gold Nanoclusters.

Aggregation-induced emission (AIE) provides an efficient strategy to synthesize highly luminescent metal nanoclusters (NCs), however, rational control of emission energy and intensity of metal NCs is still challenging. This communication reveals the impact of surface AuI -thiolate motifs on the AIE properties of Au NCs, by employing a series of water-soluble glutathione (GSH)-coordinated Au complexes and NCs as a model ([Au10 SR10 ], [Au15 SR13 ], [Au18 SR14 ], and [Au25 SR18 ]- , SR=thiolate ligand). Spectroscopic investigations show that the emission wavelength of Au NCs is adjustable from visible to the near-infrared II (NIR-II) region by controlling the length of the AuI -SR motifs on the NC surface. Decreasing the length of AuI -SR motifs also changes the origin of cluster luminescence from AIE-type phosphorescence to Au0 -core-dictated fluorescence. This effect becomes more prominent when the degree of aggregation of Au NCs increases in solution.

Unraveling the Mechanism of the Brust-Schiffrin Formation of Au25(SR)18 through Mass Spectrometry.

The Brust-Schiffrin (BS) method for gold nanoparticle (Au NP) synthesis is celebrated for its ability to produce highly monodisperse NPs from toluene-water solutions, in contrast to aqueous methods, such as the Turkevich method. Despite the method's success, the actual formation mechanisms remain largely unknown due to difficulty in studying the intermediates with species-differentiating techniques such as mass spectrometry (MS) or nuclear magnetic resonance (NMR). The issue lies in the use of solvents poorly compatible with these techniques and the difficulty in differentiating useful intermediate species from side products and impurities in such one-pot reactions. Herein, we use our recently formulated fully aqueous BS reaction to study the formation mechanisms. MS is chiefly employed to capture the intermediate species, and the Au25(SR)18 nanocluster is used as a thermodynamically reliable end-point. We find that the BS method may comprise a unilateral complex-shedding stage in addition to the known thiol-etching stage.

Photoluminescent Characterization of Metal Nanoclusters: Basic Parameters, Methods, and Applications.

Metal nanoclusters (MNCs) can be synthesized with atomically precise structures and molecule formulae due to the rapid development of nanocluster science in recent decades. The ultrasmall size range (normally < 2 nm) endows MNCs with plenty of molecular-like properties, among which photoluminescent properties have aroused extensive attention. Tracing the research and development processes of luminescent nanoclusters, various photoluminescent analysis and characterization methods play a significant role in elucidating luminescent mechanism and analyzing luminescent properties. In this review, it is aimed to systematically summarize the normally used photoluminescent characterizations in MNCs including basic parameters and methods, such as excitation/emission wavelength, quantum yield, and lifetime. For each key parameter, first its definition and meaning is introduced and then the relevant characterization methods including measuring principles and the revelation of luminescent properties from the collected data are discussed. Then, it is discussed in details how to explore the luminescent mechanism of MNCs and construct NC-based applications based on the measured data. By means of these characterization strategies, the luminescent properties of MNCs and NC-based designs can be explained quantitatively and qualitatively. Hence, this review is expected to provide clear guidance for researchers to characterize luminescent MNCs and better understand the luminescent mechanism from the measured results.

Cation polymer-induced aggregation of water-soluble Au(I)-thiolate complexes and their photoluminescence properties.

Au(I)-thiolate complexes are a new class of aggregation-induced emission (AIE) material. Here we demonstrate a new aggregation strategy of water-soluble Au(I)-thiolate complexes induced by cationic polymers at optimized pH values. The generated AIE shows longer wavelengths than the emission induced by other methods.

Electrocatalysis of gold-based nanoparticles and nanoclusters.

Gold (Au)-based nanomaterials, including nanoparticles (NPs) and nanoclusters (NCs), have shown great potential in many electrocatalytic reactions due to their excellent catalytic ability and selectivity. In recent years, Au-based nanostructured materials have been considered as one of the most promising non-platinum (Pt) electrocatalysts. The controlled synthesis of Au-based NPs and NCs and the delicate microstructure adjustment play a vital role in regulating their catalytic activity toward various reactions. This review focuses on the latest progress in the synthesis of efficient Au-based NP and NC electrocatalysts, highlighting the relationship between Au nanostructures and their catalytic activity. This review first discusses the parameters of Au-based nanomaterials that determine their electrocatalytic performance, including composition, particle size and architecture. Subsequently, the latest electrocatalytic applications of Au-based NPs and NCs in various reactions are provided. Finally, some challenges and opportunities are highlighted, which will guide the rational design of Au-based NPs and NCs as promising electrocatalysts.

Engineering ultrasmall metal nanoclusters for photocatalytic and electrocatalytic applications.

In view of many of the fundamental properties of ultrasmall noble metal nanoclusters progressively being uncovered, it has become increasingly clear that this class of materials has enormous potential for photocatalytic and electrocatalytic applications due to their unique electronic and optical properties. In this Minireview, we highlight the key electronic and optical properties of metal nanoclusters which are essential to photocatalysis and electrocatalysis. We further use these properties as the basis for our discussion to map out directions or principles for the rational design of high performance photocatalysts and electrocatalysts, highlighting several successful attempts along this direction.