Polyoxometalate Derivatives with Multiple Organic Groups. 2. Synthesis and Structures of Tris(organotin) alpha, beta-Keggin Tungstosilicates

Eight tris(organotin)-substituted Keggin tungstosilicate heteropolyanions have been synthesized and characterized by elemental analysis, infrared and M?ssbauer spectroscopy, multinuclear NMR, and X-ray crystallography. The new anions contain alpha- or beta-SiW(9)O(34)(10)(-) moieties and are of two structural types, [(RSn)(3)(SiW(9)O(37))](7)(-) (R, isomer: Ph, alpha-, 1; n-Bu, alpha-, 2; Ph, beta-, 3; n-Bu, beta-, 4) and [(RSnOH)(3)(SiW(9)O(34))(2)](14)(-) (Ph, alpha-, 5; n-Bu, alpha-, 6; Ph, beta-, 7; n-Bu, beta-, 8). Crystals of Cs(4)H(3)[(PhSn)(3)(SiW(9)O(37))].8H(2)O (anion 3) are monoclinic, space group C2/c, with lattice constants a = 48.91(2) ?, b = 12.111(3) ?, c = 20.334(9) ?, beta = 102.30 degrees, and Z = 8. The anion has nominal C(3)(v)() symmetry and has a structure with three corner-shared WO(6) octahedra of the beta-Keggin anion replaced by three PhSnO(5) groups. Crystals of Cs(9)H(5)[(BuSnOH)(3)(SiW(9)O(34))(2)].36H(2)O (anion 6) are tetragonal, space group P&fourmacr;2(1)m, with lattice constants a = b = 29.005(4) ?, c = 13.412(4) ?, and Z = 4. The anion has the anticipated D(3)(h)() symmetry and contains three BuSnOH groups sandwiched between A,alpha-SiW(9)O(34)(10)(-) anions.     

Deactivation of vibrationally excited ozone by O(3P) atoms

Using laser-induced fluorescence of ozone (to measure the rate of disappearance of O₃²) and NO₂ titration (to determine O atom concentrations), we have determined bimolecular rate constants for the deactivation by O(³P atoms) of ozone in excited stretching and bending modes. These experiments do not distinguish between deactivation by (a) the exchange of vibrational and translational energy or (b) the chemical reaction O₃ + O → 2O₂. If the non-reactive pathway (a) is assumed to dominate, then O(³P) is 150 times more effective than O₂ in deactivating O²₃. If chemical reaction (b) is dominant, the bimolecular rate constant for O²₃ + O(³P) is larger by a factor of 150–1500 than that for ground-state ozone.     

p-Alkoxy- and p-alkylbenzoates of α, a'-bi-p-hydroxytoluene. New series of liquid-crystalline compounds

Abstract

Six p-alkoxy and eight p-alkylbenzoates of 1,2-(p-hydroxyphenyl)ethane were synthesized for potential use as stationary phases in gas-liquid chromatography. All the p-alkoxy derivatives were nematic. The first five members of the alkyl series were nematic and the rest exhibited both smectic and nematic character. Most possess the desired combination of a wide liquid-crystalline temperature range and a high mesomorphic-isotropic transition temperature. The nematic-isotropic transition temperatures and entropies show the usual alternations characteristic of a high-melting series.     

Cascade assembly of the benzo[a]anthraquinone ring system common to the angucycline antibiotics

A benzo[a]anthraquinone ring system, common to a group of angucycline antibiotics, has been prepared by a unique cascade of reactions. The reaction sequence was initiated by a Suzuki-Miyaura cross-coupling between a bromoquinone and vinyl boronic anhdyride. The reaction product is proposed to undergo a 6π-electron cyclization triggered by reductive activation of the quinone. The reaction process is proposed to be autocatalytic.     

Anomalous behaviour of hyperfine fields at iron in new magnetic systems RuxFey Si and RuFeB

A new class of magnetic system Ru_xFe_ySi, has been identified in which the hyperfine field at Fe, as sensed by⁵⁷Fe Mossbauer effect, is seen to evolve at a characteristic temperature far below the bulk magnetic ordering temperatures.     

RuFeSi — A new magnetic system

A ternary system consisting of Ru, Fe and Si is identified in which the hyperfine field at Fe is seen to evolve at a characteristic temperature, T¹, far below the magnetic ordering temperature, T_m. It is speculated that the magnetic ordering at T_m is itinerant and T¹ corresponds to the localization of the majority spin electrons at the Fe atoms.     

On critical exponents for some quasilinear parabolic equations

We study the Cauchy problem for the quasilinear parabolic equation where p > 1 is a parameter and ψ is a smooth, bounded function on (1, ∞) with ? ? sψ′(s)/ψ(s) ? θ for some θ > 0. If 1 < p < 1 + 2/N, there are no global positive solutions, whereas if p > 1 + 2/N, there are global, positive solutions for small initial data.     

A time domain analysis of wave motions in chiral materials

A time domain analysis of the equations governing wave propagation in an unbounded chiral medium is presented by a spectral family approach and by a direct eigenfunction expansion using Beltrami–Moses fields.     

A lattice gas model for thermohydrodynamics

The lattice gas model is extended to include a temperature variable in order to study thermohydrodynamics, the combination of fluid dynamics and heat transfer. The compressible Navier-Stokes equations are derived using a Chapman-Enskog expansion. Heat conduction and convection problems are investigated, including Bénard convection. It is shown that the usual rescaling procedure can be avoided by controlling the temperature.