We prepare a series of MAg 24 (SR) 18 (M = Ag/Pd/ Pt/Au) nanoclusters (NCs) with similar core−inner shell−outer shell structures and investigate their crystal and solution photoluminescence. The core silver atom replacement by the Pd/Pt/Au atom obviously tunes the geometric and electronic structures of Ag 25 (SR) 18 NC. The crystal photoluminescence intensities sequence hints a core-atom-directing charge transfer from the ligands to the metal kernels. Both the calculated NPA charge and the measured Ag inner shell −S terminal bond length support the proposed mechanism. Further experiments show the solvent influence on the NCs photoluminescence supported by the blue-shift of emissions of MAg 24 (SR) 18 NCs and the solvent-dependent photoluminescence intensity sequences. Especially, for PtAg 24 (SR) 18 , the quantum yield is almost 100-fold greater in CH 3 CN (18.6%) than in CH 2 Cl 2 (0.2%). However, the emission wavelengths of the series of NCs are barely influenced by the solvent type. This work indicates the importance of the core atom and the solvent to the photoluminescence of core−inner shell−outer shell silver NCs, having important implications for the photoluminescence mechanisms and tuning of noble metal nanoparticles.

Alloy nanoparticles with atomic monodispersity is of importance for some fundamental research (e.g., the investigation of active sites). However, the controlled preparation of alloy nanoparticles with atomic monodispersity has long been a major challenge. Herein, for the first time a unique method, antigalvanic reduction (AGR), is introduced to synthesize atomically monodisperse Au25Ag2(SC2H4Ph)18 in high yield (89%) within 2 min. Interestingly, the two silver atoms in Au25Ag2(SC2H4Ph)18 do not replace the gold atoms in the precursor particle Au25(SC2H4Ph)18 but collocate on Au25, which was supported by experimental and calculated results. Also, the two silver atoms are active to play roles in stabilizing the alloy nanoparticle, triggering the nanoparticle fluorescence and catalyzing the hydrolysis of 1,3-diphenylprop-2-ynyl acetate.

Metal nanoclusters have recently attracted extensive interest not only for fundamental scientific research, but also for practical applications. For fundamental scientific research, it is of major importance to explore the internal structure and crystallographic arrangement. Herein, we synthesize a gold nanocluster whose composition is determined to be Au60S6(SCH2Ph)36 by using electrospray ionization mass spectrometry and single crystal X-ray crystallography (SCXC). SCXC also reveals that Au60S6(SCH2Ph)36 consists of a fcc-like Au20 kernel protected by a pair of giant Au20S3(SCH2Ph)18 staple motifs, which contain 6 tetrahedral-coordinate μ4-S atoms not previously reported in the Au–S interface. Importantly, the fourth crystallographic closest-packed pattern, termed 6H left-handed helical (6HLH) arrangement, which results in the distinct loss of solid photoluminescence of amorphous Au60S6(SCH2Ph)36, is found in the crystals of Au60S6(SCH2Ph)36. The solvent-polarity-dependent solution photoluminescence is also demonstrated. Overall, this work provides important insights about the structure, Au–S bonding and solid photoluminescence of gold nanoclusters.

The structural features that render gold nanoclusters intrinsically fluorescent are currently not well understood. To address this issue, highly fluorescent gold nanoclusters have to be synthesized, and their structures must be determined. We herein report the synthesis of three fluorescent Au24 (SR)20 nanoclusters (R=C2 H4 Ph, CH2 Ph, or CH2 C6 H4 (t) Bu). According to UV/Vis/NIR, differential pulse voltammetry (DPV), and X-ray absorption fine structure (XAFS) analysis, these three nanoclusters adopt similar structures that feature a bi-tetrahedral Au8 kernel protected by four tetrameric Au4 (SR)5 motifs. At least two structural features are responsible for the unusual fluorescence of the Au24 (SR)20 nanoclusters: Two pairs of interlocked Au4 (SR)5 staples reduce the vibration loss, and the interactions between the kernel and the thiolate motifs enhance electron transfer from the ligand to the kernel moiety through the Au-S bonds, thereby enhancing the fluorescence. This work provides some clarification of the structure-fluorescence relationship of such clusters.

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.

The 18-electron shell closure structure of Au nanoclusters protected by thiol ligands has not been reported until now. Herein, we synthesize a novel nanocluster bearing the same gold atom number but a different thiolate number as another structurally resolved nanocluster Au44(TBBT)28 (TBBTH = 4-tert-butylbenzenelthiol). The new cluster was determined to be Au44(2,4-DMBT)26 (2,4-DMBTH = 2,4-dimethylbenzenethiol) using multiple techniques, including mass spectrometry and single crystal X-ray crystallography (SCXC). Au44(2,4-DMBT)26 represents the first 18-electron closed-shell gold nanocluster. SCXC reveals that the atomic structure of Au44(2,4-DMBT)26 is completely different from that of Au44(TBBT)28 but is similar to the structure of Au38Q. The arrangement of staples (bridging thiolates) and part of the Au29 kernel atom induces the chirality of Au44(2,4-DMBT)26. The finding that a small portion of the gold kernel exhibits chirality is interesting because it has not been previously reported to the best of our knowledge. Although Au44(2,4-DMBT)26 bears an 18-electron shell closure structure, it is less thermostable than Au44(TBBT)28, indicating that multiple factors contribute to the thermostability of gold nanoclusters. Surprisingly, the small difference in Au/thiolate molar ratio between Au44(2,4-DMBT)26 and Au44(TBBT)28 leads to a dramatic distinction in Au 4f X-ray photoelectron spectroscopy, where it is found that the charge state of Au in Au44(2,4-DMBT)26 is remarkably more positive than that in Au44(TBBT)28 and even slightly more positive than the charge states of gold in Au-(2,4-DMBT) or Au-TBBT complexes.

Studying the kernel evolution pattern of gold nanoclusters is intriguing but challenging due to the difficulty of precise size control and structure resolution. Herein, we successfully synthesized two novel gold nanoclusters, Au(S-c-CH) and Au(S-c-CH) (S-c-CH: cyclohexanethiolate), and resolved their structures. Interestingly, it was found that the kernel evolves from Au(S-c-CH) to Au(S-c-CH) and Au(S-c-CH) in a novel fashion: alternate single-stranded evolution at both ends, which is remarkably different from the reported double-stranded growth at the bottom for the 4-tert-butylbenzenethiolate (TBBT)-protected nanocluster series. This work illustrates the variety of kernel evolution patterns and the directionality of the ligands with respect to the evolution of the kernel. In addition, differential pulse voltammetry (DPV) revealed that the electrochemical gap between the first oxidation and the first reduction potential decreases as the size increases from Au(S-c-CH) to Au(S-c-CH) and Au(S-c-CH).

Surface single-atom tailoring of a gold nanoparticle, that is, adding, removing, or replacing one surface atom on a structure-resolved nanoparticle in a controlled manner, is very exciting yet challenging and has not been hitherto achieved. Herein we report the first realization of the introduction of a single sulfur atom onto the surface of the structure-unraveled AuS(SCHPh) nanoparticle. Single-crystal X-ray crystallography reveals that the as-obtained nanoparticle consists of one Au kernel protected by one AuS(SCHPh) and one unprecedented AuS(SCHPh) motif with the introduced sulfur atom included as a tetrahedral-coordinated μ-S. The introduced sulfur leads to the changes of both internal structure and crystallographic arrangement. Unlike the case of 6HLH arrangement in AuS(SCHPh) crystals, the "ABAB" arrangement in AuS(SCHPh) crystals enhances the solid photoluminescence of amorphous AuS(SCHPh) and brings a slight redshift of the maximum emission. The extensive near-infrared emission provides AuS(SCHPh) potential applications in some fields such as anticounterfeiting, imaging, etc.