Probing the limits of steric constraints in the oligomerization of copper(I) complexes: structures of two sterically congested oligomers

Oligomeric copper(I) clusters are formed by the insertion reaction of copper(I) aryloxides into heterocumulenes. The effect of varying the steric demands of the heterocumulene and the aryloxy group on the nuclearity of the oligomers formed has been probed. Reactions with copper(I)2-methoxyphenoxide and copper(I)2-methylphenoxide with PhNCS result in the formation of hexameric complexes hexakis[N-phenylimino(aryloxy)methanethiolato copper(I)] 3 and 4 respectively. Single crystal X-ray data confirmed the structure of 3. Similar insertion reactions of CS2 with the copper(I) aryloxides formed by 2,6-di-tert-butyl-4-methylphenol and 2,6-dimethylphenol result in oligomeric copper(I) complexes 7 and 8 having the (aryloxy)thioxanthate ligand. Complex 7 was confirmed to be a tetramer from single crystal X-ray crystallography. Reactions carried out with 2-mercaptopyrimidine, which has ligating properties similar to N-alkylimino(aryloxy)methanethiolate, result in the formation of an insoluble polymeric complex 11. The fluorescence spectra of oligomeric complexes are helpful in determining their nuclearity. Ir has been shown that a decrease in the steric requirements of either the heterocumulene or aryloxy parts of the ligand can compensate for steric constraints acid facilitate oligomerization. (C) 1999 Elsevier Science Ltd. All rights reserved.

On the Limits of Spatial Reuse and Cooperative Communication for Dense Wireless Networks

We consider a dense ad hoc wireless network comprising n nodes confined to a given two dimensional region of fixed area. For the Gupta-Kumar random traffic model and a realistic interference and path loss model (i.e., the channel power gains are bounded above, and are bounded below by a strictly positive number), we study the scaling of the aggregate end-to-end throughput with respect to the network average power constraint, P macr, and the number of nodes, n. The network power constraint P macr is related to the per node power constraint, P macr, as P macr = np. For large P, we show that the throughput saturates as Theta(log(P macr)), irrespective of the number of nodes in the network. For moderate P, which can accommodate spatial reuse to improve end-to-end throughput, we observe that the amount of spatial reuse feasible in the network is limited by the diameter of the network. In fact, we observe that the end-to-end path loss in the network and the amount of spatial reuse feasible in the network are inversely proportional. This puts a restriction on the gains achievable using the cooperative communication techniques studied in and, as these rely on direct long distance communication over the network.

Microscopic description of the evolution of the local structure and an evaluation of the chemical pressure concept in a solid solution

Extended x-ray absorption fine-structure studies have been performed at the Zn K and Cd K edges for a series of solid solutions of wurtzite Zn1-xCdxS samples with x = 0.0, 0.1, 0.25, 0.5, 0.75, and 1.0, where the lattice parameter as a function of x evolves according to the well-known Vegard's law. In conjunction with extensive, large-scale first-principles electronic structure calculations with full geometry optimizations, these results establish that the percentage variation in the nearest-neighbor bond distances are lower by nearly an order of magnitude compared to what would be expected on the basis of lattice parameter variation, seriously undermining the chemical pressure concept. With experimental results that allow us to probe up to the third coordination shell distances, we provide a direct description of how the local structure, apparently inconsistent with the global structure, evolves very rapidly with interatomic distances to become consistent with it. We show that the basic features of this structural evolution with the composition can be visualized with nearly invariant Zn-S-4 and Cd-S-4 tetrahedral units retaining their structural integrity, while the tilts between these tetrahedral building blocks change with composition to conform to the changing lattice parameters according to the Vegard's law within a relatively short length scale. These results underline the limits of applicability of the chemical pressure concept that has been a favored tool of experimentalists to control physical properties of a large variety of condensed matter systems.

A computer study of the miscibility limits of Sb1bTe1bBi

The quaternary system Sb1bTe1bBi1bSe with small amounts of suitable dopants is of interest for the manufacture of thermoelectric modules which exhibit the Peltier and Seebeck effects. This property could be useful in the production of energy from the thermoelectric effect. Other substances are bismuth telluride (Bi2Te3) and Sb1bTe1bBi and compounds such as ZnIn2Se4. In the present paper the application of computer programs such as MIGAP of Kaufman is used to indicate the stability of the ternary limits of Sb1bTe1bBi within the temperature ranges of interest, namely 273 K to 300 K.

A computer study of the miscibility limits of Pd-Cu-Si

Metallic glasses are of interest because of their mechanical properties. They are ductile as well as brittle. This is true of Pd77.5Cu6Si16.5, a ternary glassy alloy. Actually, the most stable metallic glasses are those which are alloys of noble or transition metals A general formula is postulated as T70–80G30-20where T stands for one or several 3d transition elements, and includes the metalloid glass formers. Another general formula is A3B to A5B where B is a metalloid. A computer method utilising the MIGAP computer program of Kaufman is used to calculate the miscibility gap over a range of temperatures. The precipitation of a secondary crystalline phase is postulated around 1500K. This could produce a dispersed phase composite with interesting high temperature-strength properties.

A computer study of the miscibility limits of Sb-Te-Bi

The quaternary system Sb1bTe1bBi1bSe with small amounts of suitable dopants is of interest for the manufacture of thermoelectric modules which exhibit the Peltier and Seebeck effects. This property could be useful in the production of energy from the thermoelectric effect. Other substances are bismuth telluride (Bi2Te3) and Sb1bTe1bBi and compounds such as ZnIn2Se4. In the present paper the application of computer programs such as MIGAP of Kaufman is used to indicate the stability of the ternary limits of Sb1bTe1bBi within the temperature ranges of interest, namely 273 K to 300 K.