Fluorescent nanoclusters are an emerging class of modular nanomaterials. This review highlights recent developments in tailoring the photo-luminescence of nanoclusters.

Atomically precise alloy nanoclusters have been continuously appealing to scientists owing to their tunable electronic/geometric structures and enriched physicochemical properties.

Noble metal nanoclusters are in the intermediate state between discrete atoms and plasmonic nanoparticles and are of significance due to their atomically accurate structures, intriguing properties, and great potential for applications in various fields. In addition, the size-dependent properties of nanoclusters construct a platform for thoroughly researching the structure (composition)-property correlations, which is favorable for obtaining novel nanomaterials with enhanced physicochemical properties. Thus far, more than 100 species of nanoclusters (mono-metallic Au or Ag nanoclusters, and bi- or tri-metallic alloy nanoclusters) with crystal structures have been reported. Among these nanoclusters, Au25(SR)18-the brightest molecular star in the nanocluster field-is capable of revealing the past developments and prospecting the future of the nanoclusters. Since being successfully synthesized (in 1998, with a 20-year history) and structurally determined (in 2008, with a 10-year history), Au25(SR)18 has stimulated the interest of chemists as well as material scientists, due to the early discovery, easy preparation, high stability, and easy functionalization and application of this molecular star. In this review, the preparation methods, crystal structures, physicochemical properties, and practical applications of Au25(SR)18 are summarized. The properties of Au25(SR)18 range from optics and chirality to magnetism and electrochemistry, and the property-oriented applications include catalysis, chemical imaging, sensing, biological labeling, biomedicine and beyond. Furthermore, the research progress on the Ag-based M25(SR)18 counterpart (i.e., Ag25(SR)18) is included in this review due to its homologous composition, construction and optical absorption to its gold-counterpart Au25(SR)18. Moreover, the alloying methods, metal-exchange sites and property alternations based on the templated Au25(SR)18 are highlighted. Finally, some perspectives and challenges for the future research of the Au25(SR)18 nanocluster are proposed (also holding true for all members in the nanocluster field). This review is directed toward the broader scientific community interested in the metal nanocluster field, and hopefully opens up new horizons for scientists studying nanomaterials. This review is based on the publications available up to March 2018.

We report the X-ray structure of a selenolate-capped Au24(SeR)20 nanocluster (R = C6H5). It exhibits a prolate Au8 kernel, which can be viewed as two tetrahedral Au4 units cross-joined together without sharing any Au atoms. The kernel is protected by two trimeric Au3(SeR)4 staple-like motifs as well as two pentameric Au5(SeR)6 staple motifs. Compared to the reported gold-thiolate nanocluster structures, the features of the Au8 kernel and pentameric Au5(SeR)6 staple motif are unprecedented and provide a structural basis for understanding the gold-selenolate nanoclusters.

The properties of metal materials can be greatly enriched by including various elements to generate alloys. The galvanic replacement represents a classical method for the preparation of both bulk-and nanoalloy materials. The difference of the electrochemical potential between the two metals acts as the driving force for the galvanic replacement reaction. However, this classical rule partially fails at the ultrasmall size scale, for that novel chemistry emerges by the decrease of the size of materials down to less than 3 nm due to the strong quantum effect. In this Account, we discuss an emerging topic of nanochemistry, the metal exchange in atomically precise ultrasmall (<3 nm) metal nanoparticles (or nanoclusters). The metal exchange method uses different types of metal sources (e.g., AuBrPPh 3 or AgSR complexes) to react with templating metal nanoclusters (e.g., Au 25 (SR) 18 − ), and finally alloy nanoclusters are produced. We demonstrate that the metal exchange reaction between metal nanoclusters and metal complexes does not follow the classical metal activity sequence (i.e., Fe > Cd > Co > Ni > Pb > Cu > Hg > Ag > Pd > Pt > Au) and such metal exchange reactions in the nanocluster range is, to a large extent, related with the electron shell closing and the structural stability of nanoclusters.In the subsequent sections, we present effective control over the number, position, and distribution of the dopants. The shape and structure of the final alloy products can be tailored by recently developed metal exchange methods. More importantly, modulation and enhancement of the properties of NCs through metal exchange are realized. For example, the largely increased quantum yield and the significantly improved catalytic activity. In addition, we shall also discuss the real-time characterization of the metal exchange reaction by the combination of UV−vis absorption spectroscopy, high resolution electrospray ionization mass spectrometry (ESI-MS), matrix assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS), and single crystal X-ray diffraction (SC-XRD). By controlling the charge of the templating metal nanoclusters and the different types of metal complexes, the driving force of metal exchange has been studied, which is considered to be the thermodynamics rather than the electrochemical potential. In summary, the metal exchange reactions in the ultrasmall nanocluster range are totally different compared with the case of larger-sized metal nanoparticles. Depending on this novel method, atomically precise alloy nanoclusters can be prepared by reacting the nanocluster composed of inert metal (such as Au) with complexes of high-activity metals (e.g., Cd/Hg/Cu/Ag). We anticipate that future research on the metal exchange will contribute to the fundamental understanding of reaction behavior of metal atoms in ultrasmall nanoclusters and to the design of alloy nanoclusters with enhanced properties.

No abstract

Owing to their atomically precise structures, metal nanoclusters have always served as model molecular tools to dissect nanoparticle surface chemistry and to investigate structure−property correlations. Ligand exchange of the well-defined nanoclusters, occupying a significant position in the nanoparticle conversion chemistry, allows for an atomic-level knowledge and understanding of the structural transformations and the corresponding property variations. This review covers recent advances of the ligand exchange of atomically precise nanoclusters. We first present the structural transformations induced by ligand exchange, ranging from homo-gold/silver/copper nanoclusters to alloyed nanoclusters. The ligand effects in reshaping nanoclusters are disclosed as well. We further discuss the accurate conversion routes of these ligand-exchange induced structure transformations. Then, we elaborate on the ligand-exchange induced property variations, such as optical absorptions, fluorescence, catalysis, stability, magnetism, and so on. At the end of this review, the current challenges in researching the ligand exchange of nanoclusters, as well as some personal perspectives toward the future of this field, are proposed. This review hopefully provides researchers attempting to study the ligand exchange of metal nanoclusters with a synthetic toolbox of techniques that will offer more tailor-made approaches to transform nanoclusters over compositions and constructions. This review is based on publications available up to August 2019.

Herein, we report the synthesis and atomic structure of the cluster-assembled [Au60Se2(Ph3P)10(SeR)15](+) material. Five icosahedral Au13 building blocks from a closed gold ring with Au-Se-Au linkages. Interestingly, two Se atoms (without the phenyl tail) locate in the center of the cluster, stabilized by the Se-(Au)5 interactions. The ring-like nanocluster is unprecedented in previous experimental and theoretical studies of gold nanocluster structures. In addition, our optical and electrochemical studies show that the electronic properties of the icosahedral Au13 units still remain unchanged in the penta-twinned Au60 nanocluster, and this new material might be a promising in optical limiting material. This work offers a basis for deep understanding on controlling the cluster-assembled materials for tailoring their functionalities.