The distinction between valence electrons and essentially inactive core electrons is the basis of many classifying concepts in chemistry. However, it has recently been recognized that this is an oversimplification and should, at least in some areas of chemistry, be modified. Many cases are known where cations with closed d10 configurations are subject to homoatomic interactions that influence structure and properties. A characteristic and surprisingly uniform structural feature (e.g., of a number of compounds containing monovalent coinage metals) is a clusterlike assembly of d10 cations that corresponds in geometry and bond lengths to fragments of the metal structures themselves. Further evidence for a special type of bonding in such compounds is provided by their physical properties; for example, the absorption in the UV/VIS region shows a drastic redshift and the compounds are often conductors or semiconductors. The d electrons in such cases have obviously lost their pure “core” nature. All bonding models so far proposed for such systems involve mixing of higher orbitals.

Homoatomic d10–d10 Interactions: Their Effects on Structure and Chemical and Physical Properties

This review summarizes the rich structural variety of copper and silver chalcogenide clusters with protecting ligand shells of phosphane and/or organic ligands that were generated starting out from silylated chalcogenide sources. This route turned out to be fairly selective and thus allows for the isolation of uniform, polynuclear to nanosized cluster molecules that can consist of only a few or up to hundreds of metal atoms, being bridged by the chalcogen atoms. However, all of these clusters are only kinetically stable with respect to the formation of the binary coinage metal chalcogen phases, but do not collapse into the solid M2E materials owing to the protection by bulky ligands on the surface. Upon a more detailed analysis of the development of the structural properties with the cluster size, one recognizes differences for the particular M/E combinations: whereas copper chalcogenide and silver selenide clusters show a clear tendency to approach structural patterns of the Cu2E bulk, most obvious for the Cu/Se combination, this is not visible for silver sulfide clusters, even not at the largest species with 490 silver and 302 sulfur atoms. Besides the discussion on the structures of title compounds, the review presents insight into the bonding properties, reactivity, thermal and photophysical properties. The latter can be interpreted in terms of the quantum confinement effect, thus demonstrating the clusters to be understood as intermediates between mononuclear complexes and binary bulk phases.

Chalcogenide clusters of copper and silver from silylated chalcogenide sources.

Homoatomare d10‐d10‐Wechselwirkungen — Auswirkungen auf Struktur‐ und Stoffeigenschaften

The investigation of coinage metal molecular clusters bridged by chalcogen atoms represents an area of ever increasing activity in recent chemical and material science research. This is largely due to the relatively high ionic and even higher electric conductivity of binary coinage metal chalcogenides, which leads to properties intermediate between those of semiconducting and metallic phases. In addition, the size-dependency of the chemical, physical, and structural properties of substances on going from small molecules to bulk materials is of general interest. Approaches towards the synthesis and investigation of such clusters have included the study of colloidal nanoparticles with a narrow size distribution, as well as the formation and isolation of crystalline cluster compounds amenable to structural determination by single-crystal X-ray diffraction analysis. Irrespective of the chosen synthesis route, the molecules have to be kinetically protected from decomposition to the thermodynamically favored binary phases by a suitable ligand sphere, often consisting of tertiary phosphane molecules, or a combination of phosphanes and organic groups. In this report, we concentrate on the syntheses and structural as well as physical properties of ligand-stabilized, chalcogen-bridged copper clusters, which have been comprehensively studied by means of experimental and quantum chemical investigations.

Chalcogen-Bridged Copper Clusters

Three compounds, BaDyCuTe3, K1.5Dy2Cu2.5Te5, and K0.5Ba0.5DyCu1.5Te3, were synthesized from the reaction at 850 °C of the pure elements with fluxes such as BaCl2 or a eutectic mixture of LiCl/KCl. ...

Syntheses and Crystal Structures of Three Copper Tellurides: BaDyCuTe3, K1.5Dy2Cu2.5Te5, and Acentric K0.5Ba0.5DyCu1.5Te3

Zur kenntnis von Na2Cu4S3 und KCu3Te2

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Zur kenntnis von Na2Cu4S3 und KCu3Te2