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      Silver nanoclusters: synthesis, structures and photoluminescence

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          Abstract

          This review summarizes recent advances in silver nanoclusters focusing on their controlled synthesis, crystal structures and photoluminescence.

          Abstract

          Metal nanoclusters (NCs) consist of tens to hundreds of metal atoms with a diameter of <2 nm, and have attracted significant attention due to their unique molecule-like properties, such as well-defined molecular structures, explicit HOMO–LUMO transitions, quantized charge and strong luminescence emission. Various robust synthetic protocols have been successfully applied to the preparation of metal NCs. Among metal NCs, Au NCs stay at the frontline of this research, and more structural characteristics, particular optical, catalytic and electronic properties, and related technical applications of Au NCs have been discovered in recent years. By taking guidelines from Au NC research, Ag NCs have recently received increasing attention. In this review article, we first survey recent advances in developing efficient synthetic methods for Ag NCs, highlighting the underlying physical and chemical properties that make the delicate control of their sizes and surfaces possible. In the following section, we discuss recent advances in the structural determination of Ag NCs, such as Ag 25(2,4-DMBT) 18 (2,4-DMBT: 2,4-dimethylbenzenethiolate), Ag 29(1,3-BDT) 12 (1,3-BDT: 1,3-benzenedithiolate), and Ag 44(SR) 30 (R = PhCO 2H 2, PhF, PhF 2 or PhCF 3). Structural determination will help to gain deep insight into the structure–property relationships at the molecular level. In the last part, we highlight some examples of Ag NCs to demonstrate their photoluminescence properties, which offer potential applications as photodetectors and in sensing and bio-imaging. We give a brief outlook on the future development of Ag NCs from the viewpoint of synthesis and applications.

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          Atomically Precise Colloidal Metal Nanoclusters and Nanoparticles: Fundamentals and Opportunities.

          Colloidal nanoparticles are being intensely pursued in current nanoscience research. Nanochemists are often frustrated by the well-known fact that no two nanoparticles are the same, which precludes the deep understanding of many fundamental properties of colloidal nanoparticles in which the total structures (core plus surface) must be known. Therefore, controlling nanoparticles with atomic precision and solving their total structures have long been major dreams for nanochemists. Recently, these goals are partially fulfilled in the case of gold nanoparticles, at least in the ultrasmall size regime (1-3 nm in diameter, often called nanoclusters). This review summarizes the major progress in the field, including the principles that permit atomically precise synthesis, new types of atomic structures, and unique physical and chemical properties of atomically precise nanoparticles, as well as exciting opportunities for nanochemists to understand very fundamental science of colloidal nanoparticles (such as the stability, metal-ligand interfacial bonding, ligand assembly on particle surfaces, aesthetic structural patterns, periodicities, and emergence of the metallic state) and to develop a range of potential applications such as in catalysis, biomedicine, sensing, imaging, optics, and energy conversion. Although most of the research activity currently focuses on thiolate-protected gold nanoclusters, important progress has also been achieved in other ligand-protected gold, silver, and bimetal (or alloy) nanoclusters. All of these types of unique nanoparticles will bring unprecedented opportunities, not only in understanding the fundamental questions of nanoparticles but also in opening up new horizons for scientific studies of nanoparticles.
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            Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology.

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              Atomically Precise Clusters of Noble Metals: Emerging Link between Atoms and Nanoparticles.

              Atomically precise pieces of matter of nanometer dimensions composed of noble metals are new categories of materials with many unusual properties. Over 100 molecules of this kind with formulas such as Au25(SR)18, Au38(SR)24, and Au102(SR)44 as well as Ag25(SR)18, Ag29(S2R)12, and Ag44(SR)30 (often with a few counterions to compensate charges) are known now. They can be made reproducibly with robust synthetic protocols, resulting in colored solutions, yielding powders or diffractable crystals. They are distinctly different from nanoparticles in their spectroscopic properties such as optical absorption and emission, showing well-defined features, just like molecules. They show isotopically resolved molecular ion peaks in mass spectra and provide diverse information when examined through multiple instrumental methods. Most important of these properties is luminescence, often in the visible-near-infrared window, useful in biological applications. Luminescence in the visible region, especially by clusters protected with proteins, with a large Stokes shift, has been used for various sensing applications, down to a few tens of molecules/ions, in air and water. Catalytic properties of clusters, especially oxidation of organic substrates, have been examined. Materials science of these systems presents numerous possibilities and is fast evolving. Computational insights have given reasons for their stability and unusual properties. The molecular nature of these materials is unequivocally manifested in a few recent studies such as intercluster reactions forming precise clusters. These systems manifest properties of the core, of the ligand shell, as well as that of the integrated system. They are better described as protected molecules or aspicules, where aspis means shield and cules refers to molecules, implying that they are "shielded molecules". In order to understand their diverse properties, a nomenclature has been introduced with which it is possible to draw their structures with positional labels on paper, with some training. Research in this area is captured here, based on the publications available up to December 2016.
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                Author and article information

                Contributors
                Journal
                MCFAC5
                Materials Chemistry Frontiers
                Mater. Chem. Front.
                Royal Society of Chemistry (RSC)
                2052-1537
                July 30 2020
                2020
                : 4
                : 8
                : 2205-2222
                Affiliations
                [1 ]State Key Laboratory of Materials Processing and Die & Mould Technology
                [2 ]School of Materials Science and Engineering
                [3 ]Huazhong University of Science and Technology (HUST)
                [4 ]Wuhan 430074
                [5 ]China
                [6 ]College of Chemistry and Chemistry Engineering
                [7 ]Xinxiang University
                [8 ]Xinxiang 453000
                Article
                10.1039/D0QM00117A
                2b124bb0-ba17-4b3d-8a34-fda889d4076d
                © 2020

                http://rsc.li/journals-terms-of-use

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