Surface step structure of Ag13OsO6, experimental evidence for Ag13 cluster building blocks

The surface of single crystal Ag(13)OsO(6) has been investigated using atomic force microscopy. Growth spirals with very large flat terraces, separated by steps of equal height, have been observed. The measured step height of approximately 6.7 Angstrom corresponds to the diameter of one Ag13-icosahedron and identifies the cluster as the key structural building block.     

Über Oxoosmate(VII) Na5[OsO6] und Li5[OsO6]

On Oxoosmates(VII). Na₅[OsO₆] and Li₅[OsO₆] For the first time bluish black single crystals of Na₅[OsO₆] have been prepared. The structure was determined according to four-circle-diffractometer data. According to powder samples Li₅[OsO₆] is isotypic to Na₅[OsO₆]. Both are of the NaCl-type like Na₅[ReO₆] (space-group C2/m (No. 12, I.T.), Z = 2): Na₅[OsO₆]: a = 568.10(4), b = 975.00(6), c = 559.65(5) pm, β = 111.00° (1), 436 hkl, 4° ? Θ ? 30°, MoK, R = 2.7%, R_W = 2.6%. Li₅[OsO₆]: a = 568.10(4), b =975.00(6), c = 559,65(5) pm, β = 111.00° (1). Effective Coordination Numbers, ECoN, and the Madelung Part of Lattice Energy, MAPLE, are calculated and discussed.     

The Cluster Compounds Ag[W6Br14] and Ag2[W6Br14]

The reaction of W₆Br₁₂ with AgBr in evacuated silica tubes (temperature gradient 925 K/915 K) yielded brownish black octahedra of Ag[W₆Br₁₄] ( I ) and yellowish green platelets of Ag₂[W₆Br₁₄] ( II ) both in the low temperature zone. ( I ) crystallizes cubically (Pn3 (no. 201); a = 13.355 Å, Z = 4) and ( II ) monoclinically (P2₁/c (no. 14); a = 9.384 Å, b = 15.383 Å, c = 9.522 Å, β = 117.34°, Z = 2). Both crystal structures contain isolated cluster anions, namely [(W₆Brⁱ₈)Br^a₆]^1– and [(W₆Brⁱ₈)Br^a₆])]^2–, respectively, with the mean distances and angles: ( I ) d(W–W) = 2.648 Å, d(W–Brⁱ) = 2.617 Å, d(W–Br^a) = 2.575 Å, d(Brⁱ…Brⁱ) = 3.700 Å, d(Brⁱ…Br^a) = 3.692 Å, ∠W–Brⁱ–W = 60.78°. ( II ) d(W–W) = 2.633 Å, d(W–Brⁱ) = 2.624 Å, d(W–Br^a) = 2.613 Å, d(Brⁱ…Brⁱ) = 3.710 Å, d(Brⁱ…Br^a) = 3.707 Å, ∠W–Brⁱ–W = 60.23°. The Ag⁺ cations are trigonal antiprismatically coordinated in ( I ) with d(Ag–Br) = 2.855 Å, but distorted trigonally planar in ( II ) with d(Ag–Br) = 2.588–2.672 Å. The structural details of hitherto known compounds with [W₆Br₁₄] anions will be discussed.     

ChemInform Abstract: Quantum-Mechanical ab initio Investigation of the Transition-Metal Compounds OsO4, OsO3F2, OsO2F4, OsOF6, and OsF8

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Synthesis and Characterization of the Highly Unstable Metalloid Cluster Ag64(PnBu3)16Cl6

The reduction of (ⁿBu₃P)AgCl with LiBH(^sBu)₃ in toluene gives the metalloid silver cluster Ag₆₄(PⁿBu₃)₁₆Cl₆ ( 1 ) as dark red, temperature‐ and light‐sensitive single crystals in high yield. 1 is the largest structurally characterized metalloid silver cluster exhibiting chlorine and phosphine substituents only. The silver atoms in 1 show an overall brick‐shape arrangement, where structural resemblance to the close‐packed fcc and hcp structures is realized. Within 1 a 58 electron closed shell system is present. The light sensitivity renders 1 as a model compound for the primary seeds of the photo process, whereby this sensitivity, together with the high‐yield synthesis show that 1 is a perfect starting compound for further investigations like silver‐plating processes.     

X-ray diffraction investigations of Ag2ReCl6 and Ag2OsCl6

Complex salts Ag₂ReCl₆ and Ag₂OsCl₆ were synthesized and characterized by X-ray powder diffraction analysis, elemental analysis, and IR spectroscopy. The resulting compounds were demonstrated to be isostructural. It was found that the principal structural motif of the compounds under study is similar to that of K₂ReCl₆. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1314–1316, July, 2000.     

Ag2 and Ag3 Clusters: Synthesis,Characterization, and Interaction with DNA

Subnanometric samples, containing exclusively Ag₂ and Ag₃ clusters, were synthesized for the first time by kinetic control using an electrochemical technique without the use of surfactants or capping agents. By combination of thermodynamic and kinetic measurements and theoretical calculations, we show herein that Ag₃ clusters interact with DNA through intercalation, inducing significant structural distortion to the DNA. The lifetime of Ag₃ clusters in the intercalated position is two to three orders of magnitude longer than for classical organic intercalators, such as ethidium bromide or proflavine.     

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.