Versatile chelating behavior of benzil bis(thiosemicarbazone) in zinc, cadmium, and nickel complexes

Reactions of benzil bis(thiosemicarbazone), LH(6), with M(NO(3))(2).nH(2)O (M = Zn, Cd, and Ni), in the presence of LiOH.H(2)O, show the versatile behavior of this molecule. The structure of the ligand, with the thiosemicarbazone moieties on opposite sides of the carbon backbone, changes to form complexes by acting as a chelating molecule. Complexes of these metal ions with empirical formula [MLH(4)] were obtained, although they show different molecular structures depending on their coordinating preferences. The zinc complex is the first example of a crystalline coordination polymer in which a bis(thiosemicarbazone) acts as bridging ligand, through a nitrogen atom, giving a 1D polymeric structure. The coordination sphere is formed by the imine nitrogen and sulfur atoms, and the remaining position, in a square-based pyramid, is occupied by an amine group of another ligand. The cadmium derivative shows the same geometry around the metal ion but consists of a dinuclear structure with sulfur atoms acting as a bridge between the metal ions. However, in the nickel complex LH(6) acts as a N(2)S(2) ligand yielding a planar structure for the nickel atom. The ligand and its complexes have been characterized by X-ray crystallography, microanalysis, mass spectrometry, IR, (1)H, and (13)C NMR spectroscopies and for the cadmium complex by (113)Cd NMR in solution and in the solid state.     

Glassy behavior of electrons near metal-insulator transitions

The emergence of glassy behavior of electrons is investigated for systems close to disorder-driven and interaction-driven metal-insulator transitions. Our results indicate that Anderson localization effects strongly stabilize such glassy behavior, while Mott localization tends to suppress it. We predict the emergence of an intermediate metallic glassy phase separating the insulator from the normal metal. This effect is expected to be most pronounced for sufficiently disordered systems, in agreement with recent experimental observations.     

Unexpected single-step formation of 1,2-anti-heterodisubstituted calix[4]arenes upon alkylation of a tribenzoyl precursor

The selective preparation and complete structural characterization of a small series of 1,2-anti-heterodisubstituted calix[4]arenes has been accomplished. These compounds were obtained in two steps from unsubstituted p-tert-butylcalix[4]arene by tribenzoylation and a subsequent one-pot, two-step sequence involving alkylation with simultaneous partial deacylation, resulting in heterodisubstituted calixarenes carrying an alkyl and an aroyl group. The monoalkyl-tribenzoyl intermediate, prior to in situ deprotection, could also be isolated.     

First example of a tetra-carboxylate bridged dimanganese species

The compound [Mn(tda)(bipy)] (tda = S(CH2COO)2(2-)) features the first structurally characterized tetra-carboxylate dimanganese antiferromagnetic system with 'copper acetate' core; the binuclear units, completed by bipyridine chelates, are doubly chained by the tda anions that adopt an unprecedented mu,mu'-eta1,eta1,eta1,eta1 coordination mode.     

On the Structure of a k-Connected Graph

For a k-connected graph G, we introduce the notion of a block and construct a block tree. This construction generalizes, for , the known constructions for blocks of a connected graph. We apply the introduced notions to describe the set of vertices of a k-connected graph G such that the graph remains k-connected after deleting these vertices. We discuss some problems related to simultaneous deleting of vertices of a k-connected graph without loss of k-connectivity. Bibliography: 5 titles.     

Profile structures of TJ-II stellarator plasmas

Fine structures are found in the TJ-II stellarator electron temperature and density profiles, when they are measured using a high spatial resolution Thomson scattering system. These structures consist of peaks and valleys superimposed to a smooth average. Some irregularities remain in an ensemble average of discharges with similar macroscopic parameters such as line density, central temperature, and plasma current. They are found in all the magnetic configurations explored in plasmas heated by electron cyclotron waves. Their characteristics are shown and their possible origin is discussed.     

Uncertainty evaluation of the spectral UV irradiance evaluated by using the UVSPEC radiative transfer model

The radiative transfer models allow calculating the spectral UV irradiance from some set of measured input quantities linked with the surface reflectivity, the solar zenith angle, the ozone column and the characteristics of clouds and aerosols. The spectral irradiance yielded by a model is influenced by errors in the measurement of the input quantities. In this paper, the influences of these errors are characterized and compared with other systematic effects through an uncertainty analysis. We evaluated the uncertainty of the spectral UV irradiance rendered by the UVSPEC model, under cloudless sky conditions. In order to express the uncertainty of the output quantities (the global, direct and diffuse irradiances) in terms of the standard uncertainties of the input quantities, we used a Monte Carlo-based uncertainty propagation technique. We found that the uncertainty of the irradiance in the UV-B part of the spectrum was strongly influenced by the uncertainty attributed to the ozone column datum. Moreover, the uncertainities associated with the aerosol parameters accounted for most of the UV-A global irradiance uncertainty; the latter increased from about 4% under low aerosol conditions, up to about 14% in case of polluted air. We conclude that the UV irradiance evaluation through radiative transfer models requires paying special attention to the assessment of the aerosols properties.     

Full analogy of Sharkovsky's theorem for lower semicontinuous maps

A full analogy of the celebrated Sharkovsky cycle coexistence theorem is established for lower semicontinuous (multivalued) maps on metrizable linear continua. This result is further extended to triangular maps.     

Finite size effects on structure and magnetism in mass-selected CoPt nanoparticles

In this paper, the one-way absorption property in one-dimensional dielectric/metal photonic crystal structure with a dielectric defect layer is studied. The effects of incident angle and state of polarization on one-way absorption behaviour of the anti-resonant (AR) mode are investigated. The normally incident wave from left to right propagation is totally allowed to penetrate to the structure but right to left propagation totally reflected at the same wavelength. It is found that, with increasing of the incident angle, the AR mode shifts to the lower wavelengths and its intensity decreases. Simultaneously, another AR mode with reversed one-way property appears at higher wavelength. The one-way behaviour on absorption is observed at the both states of polarizations but is localized on different wavelengths. Those effects, are suggesting that the proposed structure can be used as a direction sense polarization splitter or reflector/antireflector device.