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The series Structure and Bonding publishes critical reviews on topics of research concerned with chemical structure and bonding. The scope of the series spans the entire Periodic Table and addresses structure and bonding issues associated with all of the elements. It also focuses attention on new and developing areas of modern structural and theoretical chemistry such as nanostructures, molecular electronics, designed molecular solids, surfaces, metal clusters and supramolecular structures. Physical and spectroscopic techniques used to determine, examine and model structures fall within the purview of Structure and Bonding to the extent that the focus is on the scientific results obtained and not on specialist information concerning the techniques themselves. Issues associated with the development of bonding models and generalizations that illuminate the reactivity pathways and rates of chemical processes are also relevant.

The individual volumes in the series are thematic. The goal of each volume is to give the reader, whether at a university or in industry, a comprehensive overview of an area where new insights are emerging that are of interest to a larger scientific audience. Thus each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years should be presented using selected examples to illustrate the principles discussed. A description of the physical basis of the experimental techniques that have been used to provide the primary data may also be appropriate, if it has not been covered in detail elsewhere. The coverage need not be exhaustive in data, but should rather be conceptual, concentrating on the new principles being developed that will allow the reader, who is not a specialist in the area covered, to understand the data presented. Discussion of possible future research directions in the area is welcomed. Review articles for the individual volumes are invited by the volume editors. Readership: research scientists at universities or in industry, graduate students Special offer For all customers who have a standing order to the print version of Structure and Bonding, we offer free access to the electronic volumes of the Series published in the current year via SpringerLink.



Historical Introduction to Gold Colloids, Clusters and Nanoparticles

Colloidal gold is a suspension of sub-micrometre-sized particles of gold in a fluid either water or an organic solvent. Although the gold colloids cannot be viewed using optical microscopy, the sol has an intense colour (red for particles less than 100 nm or blue/purple for larger particles). The unique optical, electronic and molecular recognition properties of gold colloids have attracted substantial interest in recent years. The properties and applications of colloidal gold particles strongly depend upon their size and shape. For example, rod-like particles have both transverse and longitudinal absorption peaks, and the anisotropy of their shapes influences their self-assembly. Gold colloids and nanoparticles have found applications in electron microscopy, electronics, nanotechnology, materials science and medicine. The development of straightforward syntheses of gold colloids in organic solvents has had a major impact on the field and the development of etching and focusing techniques has led to the isolation of some monodispersed crystalline samples which have been characterised at the atomic level. Simultaneously the isolation of molecular cluster compounds of gold, initially stabilised by phosphine and more recently organothiolato ligands, has resulted in the characterisation at the atomic level of metal particles with 3–100s of atoms. These developments have provided interesting insights into the relationships between colloids and clusters. As the diameters of these species approach the nanoscale, interesting chemical, physical and catalytic properties have emerged.
D. Michael P. Mingos

Phosphine-Coordinated Pure-Gold Clusters: Diverse Geometrical Structures and Unique Optical Properties/Responses

Synthetic techniques, geometrical structures, and electronic absorption spectra of phosphine-coordinated pure-gold molecular clusters (PGCs) accumulated over 40 years are comprehensively collected especially for those with unambiguous X-ray crystal structures available. Inspection of the electronic absorption spectra from geometrical aspects reveals that their optical properties are highly dependent on the cluster geometries rather than the nuclearity. Recent examples of unusual clusters that show unique color/photoluminescence properties and their utilization for stimuli-responsive modules are also presented.
Katsuaki Konishi

Gold Nanoclusters: Size-Controlled Synthesis and Crystal Structures

One of the major goals in nanoparticle research is to investigate their unique properties not seen in bulk materials or small molecules. In this chapter, we focus on a new class of gold nanoparticles (often called nanoclusters) that possess atomic precision (as opposed to conventional nanoparticles with a size distribution). The synthetic methods for obtaining atomically precise thiolate-protected gold nanocluters are first discussed, followed by the anatomy of the X-ray crystal structures of gold nanoclusters.
Chenjie Zeng, Rongchao Jin

Progress in the Synthesis and Characterization of Gold Nanoclusters

Quantum-sized, thiolate-protected gold nanoclusters (NCs) with atomic precision have attracted substantial research attention over the past decades due to their interesting optical, electronic properties and unusually high catalytic activities. However, despite the remarkable success has been made in the synthesis and characterization of gold nanoclusters, most synthetic approaches suffer from the production of a mixture of different cluster sizes and often a quite low yield of specific sized clusters. Therefore, the products have to be separated on the basis of various complicated processes. The difficulty in isolating and purifying nanoclusters has become a major obstacle to the practical applications of metal nanocluster materials. On the other hand, intensive studies have shown that the optical, electronic, and catalytic properties of gold nanoclusters are strongly dependent on the core size, composition, and structure. Thus, it is highly desirable to develop facile protocols that permit the synthesis, isolation, purification, and characterization of monodispersed, atomically precise gold nanoclusters with control over size in order to fully understand their size-dependent properties. This chapter describes the recent progress in the synthesis, characterization, and study of monodispersed gold nanoclusters.
Yizhong Lu, Wei Chen

Gold Thiolate Nanomolecules: Synthesis, Mass Spectrometry, and Characterization

This chapter summarizes the synthetic routes used for the following HS-CH2-CH2-Ph protected gold nanoclusters: Au25(SR)18, Au38(SR)24, Au40(SR)24, Au67(SR)35, Au103–105(SR)45–46, Au130(SR)50, and Au144(SR)60. The synthetic routes are based on either (a) direct synthetic route or (b) a core-size conversion route. The synthetic routes leading to the most stable clusters are discussed and the characterizational techniques used to study the products are described.
Chanaka Kumara, Vijay Reddy Jupally, Amala Dass

Size- and Ligand-Specific Bioresponse of Gold Clusters and Nanoparticles: Challenges and Perspectives

This review gives an introduction to the chemical and physical properties of gold clusters and nanoparticles (NPs) and reflects the present understanding how such particles interact with biological systems in vitro and in vivo. It will acquaint the reader with the basic principles of interaction from a chemical point of view and illustrates perspectives that arise for the application of gold nanoparticles (AuNPs) in biological environments.
Janine Broda, Günter Schmid, Ulrich Simon

Gold Clusters in the Gas Phase

Gold clusters exhibit strong size and charge state dependent variations in their properties. This is demonstrated by significant changes in their geometric structures and also in their chemical properties. Here we focus on clusters containing up to about 20 gold atoms and briefly review their structural evolution emphasising the role of isomerism and structural fluxionality. The discussion of chemical properties is limited to the interaction of gold clusters with molecular oxygen and carbon monoxide, separately, and their interaction in CO/O2 co-adsorbates on gold clusters eventually leading to CO oxidation. Whilst highlighting results obtained using different experimental approaches, special attention is given to the insights obtained using infrared multiple photon dissociation (IR-MPD) spectroscopy.
Alex P. Woodham, André Fielicke


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