Intramolecular d10-d10 interactions in heterometallic clusters of the transition metals

Weak attractive interactions between closed shell metal ions have been increasingly studied in the last few years and are generally designated as metallophilic interactions. They are best evidenced in the solid state where structural data obtained by X-ray diffraction provide precise information about the distance between the metals involved. The strength of such metal-metal interactions has been compared to that of hydrogen bonding (ca. 7-11 kcal mol(-1)) and is clearly sufficient to bring about novel bonding and structural features and confer interesting physical properties such as luminescence, polychromism, magnetism or one-dimensional electrical conductivity. The Cu(I)-Cu(I), Ag(I)-Ag(I) and Au(I)-Au(I) interactions have been increasingly observed and the latter have certainly been the most studied. Early qualitative analyses of the aurophilic attraction focused on Au-Au bonding originating from 6s, 6p and 5d orbital mixing. Numerous theoretical studies on metallophilic interactions continue to be carried out at various levels of sophistication which take into account relativistic and correlation effects to describe these van der Waals-type interactions. In this critical review, we would like to focus on the synthesis and structures of heterometallic clusters of the transition metals in which intra- rather than intermolecular d(10)-d(10) interactions are at work, in order to limit the role of packing effects. We wish to provide the reader with a comparative overview of the metal core structures resulting from or favoring metallophilic interactions but do not intend to provide a comprehensive coverage of the literature. We will first examine heterometallic clusters displaying homometallic and then heterometallic d(10)-d(10) interactions. Although the focus of this review is on d(10)-d(10) interactions involving metals from the group 11, we shall also briefly examine for comparison some complexes displaying intramolecular d(10)-d(10) interactions involving metals from other groups (188 references).     

Photoresponse at the semiconductor-electrolyte junction: Influence of the space charge region width

By varying the potential applied to a semiconductor-electrolyte junction its spectral response is modified. The definition of a reduced parameter from the ratio between two spectral responses at two different potentials is achieved. A quantitative analysis of the behaviour of the illuminated junction is then possible, as well as a comparison with the theoretical Gärtner model without the knowledge of the incident photon flux. The experimental support is provided by the n-GaP-1M HClO₄ junction where the semiconductor presents an indirect and a direct energy transition. Thus a spectral region is determined where the Gärtner model and the experimental spectrum coincide and a value of the minority carrier diffusion length (L=0.31μm) is deduced.     

Electrochemical behavior of n-and p-type GaxIn1−xP electrodes in sodium iodide liquid ammoniate at room temperature

The electrochemical behavior of p- and n-type Ga_xIn_1-xP electrodes in liquid ammoniate (NaI+3.3 NH₃) in the dark and under illumination has been investigated at room temperature. The flatband potentials of the semiconductors (SC) have been measured either by impedance determinations or by the photoperturbation method. Some specific physical parameters of the polycrystalline material have been deduced, such as E_gap, the electronic transition modes and the carrier densities. The SC behavior in water and in liquid ammoniate has been compared.     

Isoperimetric triangular enclosures with a fixed angle

In this paper, we study four variants of the famous isoperimetric problem. Given a set S of n > 2 points in the plane (in general position), we show how to compute in O(n ²) time, a triangle with maximum (or minimum) area enclosing S among all enclosing triangles with fixed perimeter and one fixed angle. We also show how to compute in O(n ²) time, a triangle with maximum (or minimum) perimeter enclosing S among all enclosing triangles with fixed area and one fixed angle. We also provide an Ω (n log n) lower bound for these problems in the algebraic computation tree model.     

Experimental study of the oxidation-reduction reaction on gold electrodes of the tungsten W(VI)/W(V) couple inside the dodecatungstosilicate anion

In this work we have proposed a qualitative mechanism for the first two steps of the reduction of the dodecatungstic anion on a gold electrode using measurements of faradaic impedance. Two types of supporting electrolyte were chosen—sulphate and perchlorate. The effect of competition with adsorbed SO₄^2? could be observed on the first reduction step. In both steps the charge transfer is related with homogeneous proton transfer reactions.