Hydrothermal Synthesis and Crystal Structure of Novel Alkali Trimolybdates

Novel alkali trimolybdates of the triclinic (M, M′)₂Mo₃O₁₀ (M = Rb; M′ = K, Cs) type were obtained through a systematic hydrothermal approach based on the reaction of MoO₃ with alkali halide solutions at 180 °C. The crystal structures were determined from X‐ray single crystal data. The alkali trimolybdates extend the family of known alkali trimolybdates in an unexpected fashion, because they contain a distorted variation of [Mo₃O₁₀]^2? chains as a key structural motif that has only been found in a single compound before, namely ethylenediammonium trimolybdate, (C₂H₁₀N₂)[Mo₃O₁₀]. The applied hydrothermal strategy is discussed in the general context of systematic pathways to polyoxomolybdates. Furthermore, the templating role of the alkali cations and their interaction with the polyoxomolybdate surroundings is compared to (C₂H₁₀N₂)[Mo₃O₁₀] in terms of electrostatic calculations.     

Time-resolved EPR studies of main chain radicals from acrylic polymers. Effects of tacticity, solvent, and side group structure on chain stiffness

Main chain polymeric radicals from several acrylic polymers, produced by laser flash photolysis at 248 nm in liquid solution, have been studied using direct detection time-resolved electron paramagnetic resonance (TREPR) spectroscopy at 9.5 GHz. Highly isotactic poly(methyl methacrylate) (i-PMMA) shows a sharp, well-resolved spectrum at about 95 degrees C. Using synthetic methodology to disrupt the tacticity of i-PMMA, we observed different fast-motion hyperfine coupling constants for the main chain radicals. By raising the temperature of observation, we returned the coupling constants to the same value as those in the highly isotactic sample. This result is related qualitatively to the degree of stiffness of the polymer chains as a function of tacticity. The concept is tested further by comparison to two other acrylic polymers with bulky side chains: poly(fluorooctyl methacrylate) (PFOMA) and poly(adamantyl methacrylate) (PAMA), whose main chain radicals show significant line broadening even at 110 degrees C. Solvent effects on both spectral appearance (the alternating line-width effect) and kinetic decays (attributed to T1 relaxation) are also presented and discussed in terms of main chain conformational motion.     

Use of transmitted color to calibrate the thickness of silicon samples

In preparing silicon-based semiconductors for transmission electron microscopy (TEM), it has been widely observed that a backlit silicon sample displays a series of colors in the thinnest regions. These colors results from absorption and optical interference of light within the silicon sample and depend upon the type of light source and the silicon sample thickness. These colors can range from deep red for thickness ≥5 μm, through orange and yellow in the thinner regions, to essentially colorless at the thinnest regions. In this work we present the first direct measurement of silicon color versus thickness and discuss the factors that influence this relationship.     

Properties of Si δ-layers embedded in GaAs

An ultrathin, a few monolayers (MLs) thick Si δ-layer, has been embedded in GaAs. The Si δ-layer properties have been electrically and structurally characterized. A conductivity transition has been observed, when going from free carrier transport in thin (1 ML) ordered δ-layers to the disordered conditions for Si δ-layers thicker than 4 MLs. Two novel emission bands are observed in photoluminescence (PL) for Si δ-layers in the width range 1–4 MLs, but solely at below bandgap excitation. The pronounced 2D properties of these δ-layers have been clearly demonstrated by an observed blue shift of the PL characterization as the thickness of the Si δ-layer is reduced. The so-derived results on the transition energies and the electronic structure are in good agreement with theoretical predictions obtained by a self-consistent approach.     

γ-Radiation produced supported metal complex catalysts : II. Cobalt carbonyl hydroformylation catalysts supported on polypropylene containing pyridine side chains

The optimum conditions necessary to prepare novel polymer supports for use in catalysis by the γ-radiation grafting of 4-vinylpyridine on to polypropylene are shown to be a total dose of 2 Mrad at a dose rate of 300 Krad h^?1 using a monomer to polymer ratio of 40 per cent mol/mol. Addition of 0.1 per cent w/v of p-tert-butylcatechol increases the grafting yield almost two fold. Comparison of the hydroformylation of 1-hexene in the presence of cobalt carbonyl supported on 4-vinylpyridine grafted on to polypropylene shows an increase in specificity, as determined by the ratio of normal/branched heptanal formed, by a factor of about 2.5 over the corresponding homogeneous catalyst. The supported system is of similar activity to the homogeneous system. The greater specificity of the supported catalyst is ascribed to the total environment surrounding the catalytically active site in which both the pyridine sidechain and the polypropylene backbone are believed to play an important role.     

Structural Investigations and Thermal Behaviour of Mercury(II) Sulfito Complexes

The crystal structures of (NH₄)[HgSO₃Cl] ( 1 ) and of (NH₄)₂[Hg(SO₃)₂] ( 2 ) were determined from single crystal diffractometer data sets. 1 : 22 °C, Pnma, Z = 4, a = 15.430(3), b = 5.525(1), c = 6.679(1) Å, R(F) = 0.0256, R_w(F²) = 0.0642 (all 1056 unique reflections). 2 : ?108 °C, P2₁2₁2₁, Z = 4, a = 6.2240(4), b = 9.3908(6), c = 13.6110(8) Å, R(F) = 0.0179, R_w(F²) = 0.0493 (all 2699 unique reflections). The structure of 1 contains bent Cl‐Hg‐SO₃ entities (site symmetry m; d(Hg‐Cl) = 2.3403(13) Å, d(Hg‐S) = 2.3636(12) Å, ∠(Cl‐Hg‐S) = 164.51(5)°, d(S‐O) 2×1.458(3) Å, 1.468(4) Å, = 1.461Å) linked to undulated ribbons parallel to the b ‐axis by intermolecular secondary bonds SO···Hg (d(O···Hg) = 2×2.595(3) Å). These ribbons in turn aggregate to layers around the bc ‐plane. The layers are stacked along the a ‐axis with interlayer distances of a /2. The structure of 2 is made up of O₃S‐Hg‐SO₃ moieties (d(Hg‐S) = 2.3935(7), 2.3935(8) Å; ∠(Hg‐S‐Hg) = 174.41(3)°; = 1.474Å), that are linked to ribbons parallel to the a axis by coordination of Hg to three remote O atoms (2.801(4) < d(Hg‐O) < 2.844(3) Å). Adjacent ribbons are joined together by an additional Hg‐O contact of 2.733(3) Å, leading to a three‐dimensional anionic framework. Both crystal structures are stabilised by disordered NH₄⁺ cations, placed between the anionic layers or in the vacancies of the framework, via moderate hydrogen bonding interactions N‐H···O with donor‐acceptor distances ranging from 2.8 to 3.2Å. 1 and 2 were further characterised by thermal analysis (TG, DSC). They start to decompose at temperatures above 130 °C.     

Accurate equilibrium structures obtained from gas-phase electron diffraction data: sodium chloride

A novel method has been developed to allow the accurate determination of equilibrium gas-phase structures from experimental data, thus allowing direct comparison with theory. This new method is illustrated through the example of sodium chloride vapor at 943 K. Using this approach the equilibrium structures of the monomer (NaCl) and the dimer (Na(2)Cl(2)), together with the fraction of vapor existing as dimer, have been determined by gas-phase electron diffraction supplemented with data from microwave spectroscopy and ab initio calculations. Root-mean-square amplitudes of vibration (u) and distance corrections (r(a) - r(e)) have been calculated explicitly from the ab initio potential-energy surfaces corresponding to the vibrational modes of the monomer and dimer. These u and (r(a) - r(e)) values essentially include all of the effects associated with large-amplitude modes of vibration and anharmonicity; using them we have been able to relate the ra distances from a gas-phase electron diffraction experiment directly to the re distances from ab initio calculations. Vibrational amplitudes and distance corrections are compared with those obtained by previous methods using both purely harmonic force fields and those including cubic anharmonic contributions, and the differences are discussed. The gas-phase equilibrium structural parameters are r(e)(Na-Cl)(monomer) = 236.0794(4) pm; r(e)(Na-Cl)(dimer) = 253.4(9) pm; and <(e)ClNaCl = 102.7(11) degrees. These results are found to be in good agreement with high-level ab initio calculations and are substantially more precise than those obtained in previous structural studies.     

Interatomic contributions to high-energy electron-molecule scattering

Within the independent atom scattering model, we derive an approximate formula for the rotationally and vibrationally averaged three-atom terms in the series expansion of the electron scattering cross section. This formula uses the atomic scattering factors as well as the atomic scattered wavefunctions as input, and rotational averaging is performed numerically. We compare our results to previous theoretical multiple scattering approaches for the molecules F(3), F(4), and SF(6) and to experimental data for TeF(6). Our results are consistent with those of previous calculations and inclusion of the three-atom term produces a dramatically better least squares fit of the TeF(6) data. The algorithm presented here is sufficiently fast and simple to be incorporated easily into existing electron diffraction codes.