Coinage Metal Nanoclusters Research Articles

Master key to coinage metal nanoclusters treasure chest: 38-metal clusters.

Atomically precise metal nanoclusters with specific chemical compositions have become a popular research topic due to their precise structures, attractive properties, and wide range of applications in various fields. Currently, among more than 100 reported metal nanoclusters with precise formulas, 38-atom coinage metal nanoclusters stand out due to their unique structural diversities, such as face-centered cubic (FCC) and body-centered cubic (BCC) arrangements. Among them, the formation of the metal cores includes vertex-sharing, face-fusion, and FCC cubes fusion. Due to their geometrical features, 38-atom coinage metal nanoclusters exhibit attractive properties, making them an ideal model for exploring structure-property relationships. Therefore, 38-atom coinage metal nanoclusters are a universal key to the treasure trove of nanoclusters, which can open almost all fields and are of great research significance. This paper focuses on the structure of 38-atom coinage metal nanoclusters and reviews the preparation and crystallization methods, excellent properties, and practical applications. Finally, future research prospects and development opportunities are provided.

Protection of Ag Clusters by Metal-Oxo Modules.

Monodisperse and atomically precise Ag nanoclusters have attracted considerable recent research interest. A conventional silver cluster usually consists of a silver metallic kernel and an organic peripheral ligand shell. Nevertheless, the present inevitable problem is the unsatisfied stability of such nanoclusters. In this concept, we will give an introduction to Ag clusters protected by metal-oxo modules, which exhibit enhanced stability and unique properties. Accordingly, three different types of clusters are summarized: (1) Ag clusters protected by mononuclear oxometallates; (2) Ag clusters protected by block-like metal-oxo clusters; (3) Ag clusters protected by hollow-like metal-oxo clusters. The aim of this concept is to offer possible general guidance and insight into future rational design of more metal-oxo clusters protected silver clusters or even other coinage metal nanoclusters.

Cu32(PET)24H8Cl2](PPh4)2: A Copper Hydride Nanocluster with a Bisquare Antiprismatic Core.

Atomically precise coinage metal (Au, Ag, and Cu) nanoclusters (NCs) have been the subject of immense interest for their intriguing structural, photophysical, and catalytic properties. However, the synthesis of Cu NCs is highly challenging because of low reduction potential and high reactivity of copper, demonstrating the need for new synthetic methods using appropriate ligand combinations. By designing a diamine-assisted synthetic strategy, here we report the synthesis and total structure characterization of a box-like dianionic Cu NC [Cu32(PET)24H8Cl2](PPh4)2 coprotected by 2-phenylethanethiolate (PET), hydride, and chloride ligands. Its crystal structure comprises a rare bisquare antiprismatic Cu14H8 core, assembled by two square antiprisms by edge sharing, followed by hydride binding. The rod-shaped Cu14H8 core is clamped by two complex Cu7(PET)11Cl and two simple Cu2PET metal ligand frameworks, constructing the complete structure of Cu32 NC. The presence, number, and location of hydrides are established by combined experimental and density functional theory results. The electronic structure calculations show the cluster as a zero-free-electron system, reproduce well the measured optical absorption spectrum, and explain the main absorption features. Furthermore, the Cu32 cluster is found to be a highly active homogeneous catalyst for C-N bond formation in aniline carbonylation reactions at room temperature. We hope that new findings in this work will stimulate and expand the research on Cu and other active metal NCs.

Development of coinage metal nanoclusters as antimicrobials to combat bacterial infections.

Infections from antibiotic-resistant bacteria have caused huge economic loss and numerous deaths over the past decades. Researchers are exploring multiple strategies to combat these bacterial infections. Metal nanomaterials have been explored as therapeutics against these infections owing to their relatively low toxicity, broad-spectrum activity, and low bacterial resistance development. Some coinage metal nanoclusters, such as gold, silver, and copper nanoclusters, can be readily synthesized. These nanoclusters can feature multiple useful properties, including ultra-small size, high catalytic activity, unique photoluminescent properties, and photothermal effect. Coinage metal nanoclusters have been investigated as antimicrobials, but more research is required to tap their full potential. In this review, we discuss multiple advantages and the prospect of using gold/silver/copper nanoclusters as antimicrobials.

Interactions of thiol and alkoxy radical with coinage metal nanoclusters

Interaction of small neutral coinage metal clusters (M19 = Ag19/Au19) with thiol/alkoxy radical (E = -SCH3, -OCH3, and -OCH2CH3) has been investigated to understand the bonding mechanism in the coinage metal−molecule junctions, which would allow to design biocompatible materials. In this study, structure, reactivity, and energy decomposition analysis (EDA) of M19−E complexes have been unravelled using density functional theory (DFT) based Perdew, Burke and Ernzerhof (PBE) method. In addition, the theory of “atoms in molecules” (AIM) has also been used characterize the nature of interaction. The calculated reactivity descriptors predict that the vertex atoms (Ag/Au) are the most reactive site for nucleophilic attack. The atoms lying at the center of each face are favourable for an electrophilic attack in both the cases. Geometrical parameters illustrate that the structure of the molecules change significantly before and after interactions. The signatures of ∇2ρ(r) and Hc for the anchoring bonds are respectively positive and negative, revealing that these bonds are partially electrostatic and covalent in nature. EDA calculation indicates that the largest contribution to the M−X (X = O/S) bond arise from ΔEorb and ΔEelstat contributions. Specifically, contribution from the orbital interaction is higher than the electrostatic contribution, which further confirms the covalent nature of the interaction.

Au60-: The Smallest Gold Cluster with the High-Symmetry Icosahedral Core Au13.

Among coinage metal nanoclusters with 55 atoms, only Ag55- and Cu55- are the geometric magic-number clusters, as both exhibit icosahedral symmetry. Au55-, however, exhibits much lower symmetry due largely to the strong relativistic bonding effect. In this study, we collect a much larger population (>10,000 isomers) of low-energy isomers of Au55- to Au60- by using the combined density-functional theory and basin-hopping global optimization method. We also include the spin-orbit effect in the density-functional theory computation to achieve simulated photoelectron spectra in quantitative fashion. Remarkably, we uncover that the Au13 core with the highest icosahedral ( Ih) symmetry emerges at the size of Au60-. Stability analysis suggests that Au57- with 58 valence electrons, an electronic magic number, is the relatively more stable cluster in the size range considered. Overall, in this size range we reveal a compromise between the trend toward having a perfect icosahedral 13-atom core and the strong relativistic bonding effect.

Surface Chemistry of Atomically Precise Coinage-Metal Nanoclusters: From Structural Control to Surface Reactivity and Catalysis.

A comprehensive understanding of chemical bonding and reactions at the surface of nanomaterials is of great importance in the rational design of their functional properties and applications. With the rapid development in cluster science, it has become clear that atomically precise metal clusters represent ideal models for resolving various important and/or unsolved issues related to surface science. This Account highlights our recent efforts on the fabrication of ligand-stabilized coinage nanoclusters with atomic precision from the viewpoint ofsurface coordination chemistry in particular. The successful synthesis of a large variety of metal clusters in our group has greatly benefitted from the development of an effective amine-assisted NaBH4 reduction method. First discussed in this Account is how the introduction of amines in the synthetic protocol enhances the long-term stability and high-yield production of Ag/Cu-based metals in air. Such a method allows the utilization of different organic ligands as surface stabilizing agents to manipulate both the core and surface structures of metal nanoclusters, helping to understand the role of surface ligands in determining the structures of metal nanoclusters. The coordination chemistry of ligands used in the synthesis of metal nanoclusters is crucial in determining their overall shape, metal arrangement, surface ligand binding structure, chirality and also metal exposure. Detailed discussions are given in the following four different systems: (1) The co-use of phosphines and thiolates with rich coordination structures (2 to 4-coordinated) helps to control the formation of a sequence of Ag nanoclusters with a near-perfectly cubic shape; (2) The metal arrangements and surface structures of AuCu clusters highly depend on metal precursors and counter cations used in the synthesis; (3) Metal clusters with intrinsic chirality are readily prepared by introducing chiral ligands or counterions, making it possible to obtain optically active enantiomers and understand the origin of chirality of metal nanoclusters; (4) The variation of metal exposure of the inner metal core of metal nanocluster can be controlled by the surface ligand coordination structure. Such capabilities to manipulate the surface structure of metal nanoclusters allow the creation of model systems for investigating the structure-reactivity relationship of metal nanomaterials. Several important examples are then discussed to highlight the importance of ligand coordination chemistry in tuning the surface reactivity and catalysis of metal nanoclusters. For example, bulky thiolates on Agare demonstrated to be more labile than small thiolates for making metal nanoclusters with both enhanced ligand exchange capability and catalysis. Alkynyl ligands can be thermally released from metal nanoclusters more easily than thiolates and halides while maintaining the overall structure, thereby serving as ideal systems for understanding the promoting effect of surface stabilizers on catalysis. Finally, we provide a perspective on the principles of surface coordination chemistry of metal nanoclusters and their potential applications with regards to catalysis of protected metal clusters.

Alkynyl Approach toward the Protection of Metal Nanoclusters.

The past decades have witnessed great advances in the synthesis, structure determination, and properties investigation of coinage metal nanoclusters. These monodisperse clusters have well-defined molecular structures, which is advantageous in correlating structures and properties. Metal nanoclusters are large molecules consisting of many components, so it is a big challenge to prepare them in a rational way. Strenuous efforts have been madeto control their geometric and electronic structures, in order to optimize their various properties. A metal nanocluster normally contains a metal core and a peripheral ligand shell. The ligands do not only function as simple stabilizing agents. It has been revealed that these ligands are able to influence the formation processes of the nanoclusters, and they may also dictate the sizes, shapes, and properties of nanoclusters. There are mainly three types of ligands that are widely used as surface anchors on coinage metal nanoclusters: thiolates, phosphines, and halides. Recent ligand engineering has extended the scope to alkynyl ligands. As alkynyl ligands are versatile in interacting with metal atoms, interesting alkynyl-metal interfacial structures including linear, L-shaped, and V-shaped staple motifs can be generated, as well as a series of novel coinage metal nanoclusters that exhibit intriguing molecular geometries. The staple motifs do not simply resemble the surface structures of thiolate-protected nanoclusters, because the incorporation of alkynyl ligands may significantly alter diverse properties of nanoclusters. Compared with thiolate-protected gold nanoclusters, alkynyl-protected ones with identical metal cores exhibit distinctly different absorption profiles and show much improved catalytic activities for semihydrogenation of alkynes. In addition, the participation of alkynyl ligands could profoundly affect the luminescent properties of nanoclusters. These "ligand effects" are mainly attributed to the different nature of alkynyl ligands, as electronic perturbation through π-conjugated units may largely modulate the electronic structure of the whole cluster. In this Account, we describe the development of coinage metal nanoclusters protected with alkynyl ligands. We will first briefly bring up the emergence of alkynyl ligands as anchoring groups on the surfaces of nanoclusters. Then we present the direct reduction method for the synthesis of the following four categories of nanoclusters: (a) gold nanoclusters with mixed-ligand shells, (b) all alkynyl-protected gold nanoclusters, (c) heterobimetallic gold nanoclusters, and (d) silver nanoclusters. Their molecular structures are described, and their various alkynyl-metal interfacial structures are compared with thiolate-metal staples. Finally, ligand effects on the properties of the clusters, including optical absorption, luminescence, and catalysis, are discussed. The alkynyl ligands play an important role in terms of both structural and property aspects. We believe this Account will attract increasing attention to alkynyl ligands, which have shown promising potential in generating new structures and properties of coinage metal nanoclusters.

Synthesis of cationically charged photoluminescent coinage metal nanoclusters by sputtering over a liquid polymer matrix

A generic green synthetic approach to synthesize photoluminescent metal nanoclusters of known plasmonic elements via sputtering on a biocompatible polymer matrix.