The X-ray structure of the trichlorocuprate of naphtho-15-crown-5 complexed potassium

The structure of the trichlorocuprate of naphtho-15-crown-5 complexed potassium has been determined by X-ray analysis. The crystal contains the complex cations [K(naphtho-15-crown-5)₂]⁺, the anion [Cu₂Cl₆]^2– and water molecules. The full composition of the compound in the solid state is represented by the formula [K(naphtho-15-crown-5)₂]₂[Cu₂Cl₆]·nH₂O), wheren3. The sandwich type cations are similar to those found previously for potassium complexes with benzo-15-crown-5. The coordination number of potassium is equal to 10; the coordination polyhedron is a 15-crown-5. The coordination number of potassium is equal to 10; the coordination polyhedron is a pentagonal antiprism. The water molecules are disordered and occupy six symmetrically independent positions with a probability of 0.5 in the crystal. The lack of close contacts between water molecules and the remaining components enabled the treatment of the complex as a clathrate. Supplementary Data relating to this article has been deposited with the British Library as Supplementary Publication No. 82154 (20 pages).     

Unconventional Metal–Framework Interaction in MgSi5

The silicon‐rich cage compound MgSi₅ was obtained by high‐pressure high‐temperature synthesis. Initial crystal structure determination by electron diffraction tomography provided the basis for phase analyses in the process of synthesis optimization, finally facilitating the growth of single crystals suitable for X‐ray diffraction experiments. The crystal structure of MgSi₅ (space group Cmme, Pearson notation oS24, a=4.4868(2) Å, b=10.1066(5) Å, and c=9.0753(4) Å) constitutes a new type of framework of four‐bonded silicon atoms forming Si₁₅ cages enclosing the Mg atoms. Two types of smaller Si₈ cages remain empty. The atomic interactions are characterized by two‐center two‐electron bonds within the silicon framework. In addition, there is evidence for multi‐center Mg?Si bonding in the large cavities of the framework and for lone‐pair‐like interactions in the smaller empty voids.     

Thermal analysis and EPR study of copper species in mordenites prepared by conventional and microwave-assisted methods

The main work of this thesis is to study and discuss flame-retardant properties of the flexible polyurethane foam (FPUF) added with borax, expanded graphite (EG), and EG/Borax as flame retardant, respectively. The thermal behavior of samples has been using thermogravimetry (TG) and differential thermogravimetry in air. The activation energies for different stages of thermal degradation are obtained following the equation of Kissinger. The flammability parameters, including limiting oxygen index, rate of heat release, total heat release, yield of CO, yield of CO₂, and smoke production rate, were recorded simultaneously. The char structure was studied by SEM, and their thermal stability and evolved gaseous products were examined by TG analysis–Fourier transform infrared spectroscopy. By analyzing these data, it was concluded that most combustion parameters of FPUF were decreased by the treatment, especially for EG/Borax treatment, which indicated a synergistic effect of flame retardancy. Meanwhile, the probable flame retardation mechanism was proposed.     

New optical properties of polyelectrolyte hydrogels

A new optically active medium for lasers — a polyelectrolyte hydrogen swollen in a mixture of water + alcohol + dye — is presented. An anomalous dependence of the absorbance on the composition of the mixture is observed. It shows a maximum which corresponds to the composition when the hydrogel starts to swell as a hydrophilic network.     

Synthesis of halo-fluoro-substituted adamantanes by electrophilic transannular cyclization of bicyclo[3.3.1]nonane dienes

3,7-Dimethylenebicyclo[3.3.1]nonane and its derivatives with a methyl or phenyl substituent in a methylene group react, with N-halosuccinimides NXS (X=Cl, Br, I) in dichloromethane in the presence of tetrabutylammonium dihydrotrifluoride or polyfluorinated alcohols via a transannular cyclization leading to the corresponding 1-fluoro- or 1-polyfluoroalkoxy-3-halomethyladamantanes. The reaction of the dienes with NXS and Bu₄N⁺H₂F₃⁻ conducted in THF, oxetane or ethylene oxide runs through a cascade addition of electrophiles (positively charged halogen atoms) and external nucleophiles (solvent molecules and halide anions) to the starting diene substrate and intermediate adamantyl carbocation.     

Efficient electrocatalytic hydrogen production from H+ ions using specially designed boron-capped cobalt clathrochelates

Specially designed hexachlorine-containing cobalt(II) tris-dioximate clathrochelates were found to efficiently electrocatalyze the production of molecular hydrogen from H(+) ions without the overpotential of this process.     

Thermochemistry of Gd2BaCuO5 and LuBa2Cu3Ox

Solution calorimetry, using 6.0 M HCl as a solvent, is used to study the thermochemistry of Gd2BaCuO5 and the high-temperature superconductor LuBa2Cu3O6.92. For the first time, the standard formation enthalpies of these phases have been determined as follows: DeltafH(o)(Gd2BaCuO 5, s, 298.15 K) = -2618.6 +/- 7.4 kJ/mol; DeltafH(o)(LuBa2Cu3O6.92, s, 298.15 K) = -2693.1 +/- 11.9 kJ/mol. The thermodynamic stability at room temperature has been assessed. The results show that Gd211 and Lu123 are thermodynamically stable with respect to binary oxides and unstable with respect to interaction with CO 2 at ambient temperatures. Lu123 is thermodynamically stable with respect to assemblages containing combinations of Lu2O3, CuO, and BaCuO2 and thermodynamically unstable with respect to interactions with water.     

TM7TM'6B8 (TM = Ta, Nb; TM' = Ru, Rh, Ir): new compounds with [B6] ring polyanions

The ternary boron compounds TM(7)TM'(6)B(8) (TM = Ta, Nb; TM' = Ru, Rh, Ir) were prepared by high-temperature thermal treatment of mixtures of the elements. An analysis of the chemical bonding by the electron density/electron localizability approach reveals formation of covalently bonded polyanions [B(6)] and [TM'(6)B(2)]. The cationic part of the structure contains separated TM cations. In agreement with the chemical bonding analysis and band structure calculations, all TM(7)TM'(6)B(8) compounds are metallic Pauli-paramagnets (TM' = Ru, Rh) or diamagnets (TM' = Ir).