A.C. electrical conductivity of pure and doped potassium perchlorate

A.C. electrical conductivity of potassium perchlorate (KP) has been measured in the temperature range 25�325°C at frequencies ranging from 50�500 Hz using an automated technique. The results are interpreted in terms of a novel mechanism involving Schottky defects in the anion sublattice and Frenkel defects in the cation sublattice. Theconductivity behavior of KP is compared with literature data on similar low-symmetry systems containing polyatomic ions.

Lack of Cu3+, Pb4+, and Bi5+ ions in metallic and superconducting oxides

With a view to understand the oxidation states of metal ions involved in oxide superconductors, oxidation behavior of Cu, Pb, and Bi metals have been studiedi employing x-ray-photoemission and ultraviolet-photoemission spectroscopy. Pb and Bi have distinct 6p (0 to 4 eV) and 6s (7.5 to 10 eV) bands and upon oxidation, only the 6p electrons are ionized forming PbO and Bi2O3 with the simultaneous development of the O2-(2p) band (3 to 7 eV). We show that the 6s band of metals lies below the O2-(2p) band, and hence 6s electrons cannot be ionized to form Pb4+ and Bi4+ as expected in PbO2, BaPbO3, BaBiO3, and BaPb0.75Bi0.25O3. Instead these oxides are stabilized with lower valent O22- along with O2- ions with metals remaining in +2 and +3 states. Similarly, it is shown that the Cu2+(3d) band overlaps with the O2-(2p) band in the YBa2Cu3O6.95 completely and the excess oxygen can be stabilized through lower valent oxide ions instead of Cu3+.

Magnetic susceptibility studies on ternary oxides of copper(II)

The magnetic susceptibilities of a large number of ternary oxides of copper having structural features common to the presently identified phases of high-temperature superconductors have been studied in the temperature range 14-300 K. The systems studied are Ln2CuOP( Ln = La, Pr, Nd, etc.), Sr2CuO2CI2,B i2Cu0,, Ca2Cu03,S r2Cu03,S rCu02, MgCu203,B a2Cu3O4CI2Y, 2Cu205,Y2BaCu0,, BaCu02, Li2Cu02, etc. Cu2+ ions take different coordinations, like isolated square planar, square pyramidal or distorted-tetrahedral and octahedral, in these compounds. These compounds also exhibit different varieties of possible magnetic superexchange interactions like 180' or 90' Cu-0-Cu or Cu-0-0-Cu types as well as direct Cu-Cu interactions. Compounds in which there are extended 180' Cu-0-Cu interactions show a low, nearly temperature-independent susceptibility (100 X lod emu/mol). The estimated value of J for the Cu-0-Cu interaction is between 800 and 1500 K in these compounds. Isolated Cu2+ ions in which there are no 180' or close to 180" Cu-0-Cu interactions show Curie-Weiss susceptibility behavior. Compounds with only Cu-0-0-Cu interaction show evidence for the onset of antiferromagnetic coupling between 30 and 50 K. The superexchange rules are useful for explaining the qualitative features of the results. The possibility of disproportionation of Cu2+ ion when there are short Cu-Cu distances as in Bi2Cu04 is discussed. The extended geometry of the copper-oxygen framework seems to be more important than the local geometry around the Cu2+ ion in determining the magnetic properties.

Complexes of lanthanide nitrates with O,O′,N-triisopropyl phosphoramidate

A substituted phosphoramidate has been used as a ligand to lanthanides for the first time. New complexes of lanthanide nitrates with O,O′,N-triisopropyl phosphoramidate (TIP) of the general formula Ln(TIP)3(NO3)3 where Ln=La-Yb and Y have been synthesised and characterised by chemical analysis, infrared and visible electronic spectra and electrical conductance.Infrared spectra indicate the coordination of the ligand to the metal ions through the oxygen of the P=O group. IR and conductance show that the nitrate groups are all coordinated. Electronic spectral shapes have been interpreted in terms of an eight coordinate geometry around the metal ions.

Effect of electric field on ammonium perchlorate decomposition

A novel method of detecting the charge-carrying species in inorganic decomposable salts is described. In ammonium perchlorate it is observed that the charge-carrying species at temperatures 150 and 230°C are oppositely charged; i.e., they are negatively charged (ClO−4 ions) at 230°C and positively charged (H+ or NH+4) at 150°C.

Synthesis, Structure and Optical Studies of a Family of Three-Dimensional Rare-Earth Aminoisophthalates M(mu(2)-OH)(C8H5NO4)] (M = Y3+, La3+, Pr3+, Nd3+, Sm3+, Eu3+, Gd3+, Dy3+, and Er3+)

A hydrothermal reaction of the acetate salts of the rare-earths, 5-aminoisophthalic acid (H(2)AIP), and NaOH at 150 degrees C for 3 days gave rise to a new family of three-dimensional rare-earth aminoisophthalates, M(mu(2)-OH)(C8H5NO4)] M = Y3+ (I), La3+ (II), Pr3+ (III), Nd3+ (IV), Sm3+ (V), Eu3+ (VI), Gd3+ (VII), Dy3+ (VIII), and Er3+ (IX)]. The structures contain M-O(H)-M chains connected by AIP anions. The AIP ions are connected to five metal centers and each metal center is connected with five AIP anions giving rise to a unique (5,5) net. To the best of our knowledge, this is the first observation of a (5,5) net in metal-organic frameworks that involve rare-earth elements. The doping of Eu3+/(3+) ions in place of Y3+/ La3+ in the parent structures gave rise to characteristic metal-centered emission (red = Eu3+, green = Tb3+). Life-time studies indicated that the excited emission states in the case of Eu3+ (4 mol-% doped) are in the range 0.287-0.490 ms and for Tb3+ (4 mol-% doped) are in the range of 1.265-1.702 ms. The Nd3+-containing compound exhibits up-conversion behavior based on two-photon absorption when excited using lambda = 580 nm.

Effect of electric field on ammonium perchlorate decomposition

A novel method of detecting the charge-carrying species in inorganic decomposable salts is described. In ammonium perchlorate it is observed that the charge-carrying species at temperatures 150 and 230°C are oppositely charged; i.e., they are negatively charged (ClO−4 ions) at 230°C and positively charged (H+ or NH+4) at 150°C.

Doping Transition Metal (Mn or Cu) Ions in Semiconductor Nanocrystals

Following growth doping strategy and using dopant oxides nanocrystals as dopant sources, we report here two different transition-metal ions doped in a variety of group II-VI semiconductor nanocrystals. Using manganese oxide and copper oxide nanocrystals as corresponding dopant sources, intense photoluminescence emission over a wide range of wavelength has been observed for different host nanocrystals. Interestingly, this single doping strategy is successful in providing such highly emissive nanocrystals considered here, in contrast with the literature reports that would suggest synthesis strategies to be highly specific to the particular dopant, host, or both. We investigate and discuss the possible mechanism of the doping process, supporting the migration of dopant ions from dopant oxide nanocrystals to host nanocrystals as the most likely scenario.

Inorganic Analogues of Graphene

The discovery of graphene has aroused great interest in the properties and phenomena exhibited by two-dimensional inorganic materials, especially when they comprise only a single, two or a few layers. Graphene-like MoS2 and WS2 have been prepared by chemical methods, and the materials have been characterized by electron microscopy, atomic force microscopy (AFM) and other methods. Boron nitride analogues of graphene have been obtained by a simple chemical procedure starting with boric acid and urea and have been characterized by various techniques that include surface area measurements. A new layered material with the composition BCN possessing a few layers and a large surface area discovered recently exhibits a large uptake of CO2.

An EQCM Investigation of Electrochemical Precipitation of Mn(OH)(2) and Its Capacitance Behavior

Electrochemical quartz crystal microbalance (EQCM) has been used to study the electrochemical precipitation of Mn(OH)(2) on a Au crystal and its capacitance properties. From the EQCM data, it is inferred that NO3- ions get adsorbed on the Au crystal and then undergo reduction, resulting in an increase in pH near the electrode surface. Precipitation of Mn2+ occurs as Mn(OH)(2), with an increase in mass of the Au crystal. Mn(OH)(2) undergoes oxidation to MnO2, which exhibits electrochemical supercapacitor behavior on subjecting to electrochemical cycling in a Na2SO4 electrolyte. EQCM data indicate mass variations corresponding to surface insertion/extraction of Na+ ions during discharge/charge cycling. (C) 2010 The Electrochemical Society. DOI: 10.1149/1.3479665] All rights reserved.

Amino acid-lanthanide interactions, Part 2. The X-ray crystal structures of lanthanide and calcium complexes of 1-amino-cyclohexane-1-carboxylic acid (Acc6)

The structures of [Nd-2(Acc(6))(H2O)(6)](ClO4)(6) .(H2O)(6) (1) [Er-2(Acc(6))(4)(H2O)(8)](ClO4)(6) .(H2O)(11) (2) and [Ca-5(Acc(6))(12)(H2O)(6)](ClO4)(10).(H2O)(4) (3) (Acc(6) = 1-aminocyclohexane-1-carboxylic acid) have been determined by X-ray crystallography. The lanthanide complexes 1 and 2 are dimeric in which two lanthanide cations are bridged by four carboxylato groups of Acc(6) molecules. In addition, the neodymium complex (1) features the unidentate coordination of the carboxyl group of an Acc(6) molecule in place of a water molecule in the erbium complex (2). The coordination number in both 1 and 2 is eight. The calcium Acc(6) complex (3) is polymeric; three different calcium environments are observed in the asymmetric unit. Two calcium ions are hexa-coordinated and one is hepta-coordinated. Considerable differences are observed between the solid state structures of Ln(III) and Ca-II complexes of Acc(6

Thiomalates of alkaline earth metals

Solid state 1:1 complexes of divalent Mg, Ca, Sr and Ba with thiomalic acid(tma) have been isolated and characterised by elemental analysis, IR spectra and thermal studies. It is shown that tma coordinates to the metal ions through carboxylic oxygen atoms. Thermal studies of these complexes show that desulphurisation preceeds decarbonylation reaction leading to the formation of metal carbonates in all the cases except Mg where MgO is the end product. Thermal stability of the anhydrous thiomaltes follows the order Mg not, vert, similar Ca > Sr > Ba. Structures have been proposed based on the information obtained from these studies.

Ions in water: Role of attractive interactions in size dependent diffusivity maximum

A molecular dynamics study of model ions in water is reported. The van der Waals diameter of both the cations and anions is varied. We have carried out two sets of simulations-with and without dispersion interaction-between the ion and water. Self-diffusivity of the ions exhibits an anomalous maximum as a function of the van der Waals diameter for both these sets. This existence of a maximum in self-diffusivity when there is no dispersion interaction between the ion and the water is attributed to the attractive term from electrostatic interactions. Detailed analysis of this effect shows that the solvent shell is more strongly defined in the presence of dispersion interactions. A smaller ion exhibits biexponential decay while a single exponential decay is seen for the ion with maximum diffusivity in the self-part of the intermediate scattering function. The solvent structure around the ion appears to determine much of the dynamics of the ion. Interesting trends are seen in the activation energies and these can be understood in terms of the levitation effect. (C) 2010 American Institute of Physics. doi:10.1063/1.3481656]

The first structurally characterized diruthenium(II,III) complex with four bridging arylcarboxylato ligands

The diruthenium(II,III) compound [Ru2Cl(O2CC6H4-p-OMe)4](H2O)0.25 (1) has been prepared and its crystal structure determined by X-ray studies. The crystals belong to the triclinic space group, PImage , and the asymmetric unit consists of one full dimer and two half dimers. The {Ru2(O2CC6H4-p-OMe)4+} units are bridged by chloride ions into an infinite zigzag chain, with an average Ru---Cl distance and Ru---Cl---Ru angle of 2.567(2) Å and 121.0(1)°, respectively. The average Ru---Ru distance of 2.286(1) Å in 1 is comparable with that in analogous tetra-alkylcarboxylates, Ru2Cl(O2CR)4 and tetra-amidates, Ru2Cl(ArCONH)4.