Contributions from the indirect ionic interactions to the elastic constants in the rock-salt structure crystals

Under the harmonic approximation, the contributions from the indirect ionic interactions to the elastic constants are calculated for the alkali halide and silver halide crystals with the rock-salt structure. The coupling constants of the indirect ionic interactions are calculated by the self-consistent field treatment of the local density approximation and the spherical solid model. The calculated values of the coupling constants are large for the silver ion. The indirect ionic interaction significantly affects the elastic constants. It quantitatively explains the deviation from the Cauchy relation in alkali halide crystals. Moreover, it provides a clear account for the large values of the deviation from the Cauchy relation in AgCl and AgBr.     

A Tin–Tungsten Mixed Oxide as an Efficient Heterogeneous Catalyst for C?C Bond‐Forming Reactions

Mix and calcinate : The tin–tungsten mixed oxide (Sn–W oxide) prepared by calcination of the Sn–W hydroxide at 800 °C acts as an effective and reusable solid catalyst for C? C bond‐forming reactions, such as the cyclization of citronellal, the Diels–Alder reaction, and the cyanosilylation of carbonyl compounds with trimethylsilyl cyanide (see scheme). The observed catalysis was truly heterogeneous, and the recovered catalyst could be reused without loss of its high catalytic performance.

     

First application of the depth profile of silica species as a tracer by fast‐atom bombardment mass spectrometry: investigation of the circulation of seawater and silica uptake by diatoms

Silica, represented by SiO₂, is the general name for the compounds composed of Si, O and H with their derivative complexes. Silica forms various chemical species in aquatic solutions, such as a monomer (Si(OH)₃O⁻), dimer (Si₂(OH)₅O), and others. These species are known to vary in their relative abundances in solution depending on the chemical and physical conditions. Silica species dissolved in seawater have been examined by fast-atom bombardment mass spectrometry (FAB-MS) to elucidate the behavior of silica and its circulation as a novel tracer reflecting the chemical and physical conditions of seawater and the bioactivity of diatoms, which take up silica. In the seawater of Tokyo Bay, silica species such as [Si(OH)₂O₂Na]⁻ ([monomer–Na]⁻), [Si₂(OH)₅O₂]⁻ ([dimer]⁻), [Si₂(OH)₄O₃Na]⁻ ([dimer–Na]⁻), [Si₄(OH)₇O₅]⁻ ([cyclic tetramer]⁻), [Si₄(OH)₆O₆Na]⁻ ([cyclic tetramer–Na]⁻), [Si₄(OH)₉O₄]⁻ ([linear tetramer]⁻) and [Si₄(OH)₈O₅Na]⁻ ([linear tetramer–Na]⁻) were observed and assigned by FAB-MS. To investigate the suitability of silica species as a tracer, the relative peak intensity ratios of silica species observed in the mass spectra, i.e. the profiles of the ratio of the linear tetramer to the cyclic tetramer (m/z 329/311) and the ratio of the dimer to the cyclic tetramer (m/z 173/311) against depth, were examined to determine the annual changes and reproducibility of the depth profiles. In particular, the depth profile of the relative ratio of the linear tetramer to the cyclic tetramer, 329/311, exhibits critical changes depending on the seawater budget. These changes in the relative ratios were identified by an experiment involving a simple sodium chloride solution system. Our measurement is expected to elucidate the dynamics of silica and its role as ‘food’ for diatoms, and we showed that speciation using mass spectrometry is a powerful tool for examining elemental behavior in nature and environmental changes. Our results suggest that a silica tracer is useful for investigating the behavior of seawater in small coastal regions and the uptake of silica by diatoms. Copyright © 2009 John Wiley & Sons, Ltd.     

Tuning membership functions of kernel fuzzy classifiers by maximizing margins

We propose two methods for tuning membership functions of a kernel fuzzy classifier based on the idea of SVM (support vector machine) training. We assume that in a kernel fuzzy classifier a fuzzy rule is defined for each class in the feature space. In the first method, we tune the slopes of the membership functions at the same time so that the margin between classes is maximized under the constraints that the degree of membership to which a data sample belongs is the maximum among all the classes. This method is similar to a linear all-at-once SVM. We call this AAO tuning. In the second method, we tune the membership function of a class one at a time. Namely, for a class the slope of the associated membership function is tuned so that the margin between the class and the remaining classes is maximized under the constraints that the degrees of membership for the data belonging to the class are large and those for the remaining data are small. This method is similar to a linear one-against-all SVM. This is called OAA tuning. According to the computer experiment for fuzzy classifiers based on kernel discriminant analysis and those with ellipsoidal regions, usually both methods improve classification performance by tuning membership functions and classification performance by AAO tuning is slightly better than that by OAA tuning.     

Two-dimensional networks based on Mn4 complex linked by dicyanamide anion: from single-molecule magnet to classical magnet behavior

Three two-dimensional (2D) network compounds based on Mn(III)/Mn(II) tetranuclear single-molecule magnets (SMMs) connected by dicyanamide (dcn-) linkers have been synthesized: [Mn4(hmp)4(Hpdm)2(dcn)2](ClO4)2 x 2 H2O x 2 MeCN (2), [Mn4(hmp)4Br2(OMe)2(dcn)2] x 0.5 H2O x 2 THF (3), [Mn4(hmp)6(dcn)2](ClO4)2 (4), where Hhmp and H2pdm are 2-hydroxymethylpyridine and pyridine-2,6-dimethanol, respectively. The [Mn4]/dcn- system appears very versatile, but enables its chemistry to be rationalized by a fine-tune of the synthetic conditions. The double cuboidal [Mn4] unit is preserved in the whole family of compounds, despite strong modifications of its Mn(II) coordination sphere. The chemical control of the coordination number of dcn- on the Mn(II) sites has been the key to obtain the following series of compounds: a discrete cluster, [Mn4(hmp)6(NO3)2(dcn)2] x 2 MeCN (1), 2D networks (2, 3, and 4), and the previously reported 3D compound, [Mn4(hmp)4(mu3-OH)2][Mn(II)(dcn)6] x 2 MeCN x THF. Direct current magnetic measurements show that both Mn2+-Mn3+ and Mn3+-Mn3+ intra-[Mn4] magnetic interactions are ferromagnetic leading to an S(T) = 9 ground state for the [Mn4] unit. Despite the very similar 2D lattices in 2-4, the two kinds of orientation of the [Mn4] unit (i.e., angle variations between the two easy axes) lead to different magnetic properties ranging from SMM behavior for 2 and 1 to a long-range canted antiferromagnetic order for 4. Compound 3 is more complicated as the magnetic measurements strongly suggest the presence of a canted antiferromagnetic order below 2.1 K, although the magnetization slow relaxation is simultaneously observed. Heat capacity measurements confirm the long-range magnetic order in 4, while in 3, the critical behavior is frozen by the slow relaxation of the anisotropic [Mn4] units.     

gamma-1,2-H2SiV2W10O40] immobilized on surface-modified SiO2 as a heterogeneous catalyst for liquid-phase oxidation with H2O2

An organic-inorganic hybrid support has been synthesized by covalently anchoring an N-octyldihydroimidazolium cation fragment onto SiO2 (denoted as 1-SiO2). This modified support was characterized by solid-state 13C, 29Si, and 31P NMR spectroscopy, IR spectroscopy, and elemental analysis. The results showed that the structure of the dihydroimidazolium skeleton is preserved on the surface of SiO2. The modified support can act as a good anion exchanger, which allows the catalytically active polyoxometalate anion [gamma-1,2-H2SiV2W10O40]4- (I) to be immobilized onto the support by a stoichiometric anion exchange (denoted as I/1-SiO2). The structure of anion I is preserved after the anion exchange, as confirmed by IR and 51V NMR spectroscopy. The catalytic performance for the oxidation of olefins and sulfides, with hydrogen peroxide (only one equivalent with respect to substrate) as the sole oxidant, was investigated with I/1-SiO2. This supported catalyst shows a high stereospecificity, diastereoselectivity, regioselectivity, and a high efficiency of hydrogen peroxide utilization for the oxidation of various olefins and sulfides without any loss of the intrinsic catalytic nature of the corresponding homogeneous analogue of I (i.e., the tetra-n-butylammonium salt of I, TBA-I), although the rates decreased to about half that with TBA-I. The oxidation can be stopped immediately by removal of the solid catalyst, and vanadium and tungsten species can hardly be found in the filtrate after removal of the catalyst. These results rule out any contribution to the observed catalysis from vanadium and tungsten species that leach into the reaction solution, which means that the observed catalysis is truly heterogeneous in nature. In addition, the catalyst is reusable for both epoxidation and sulfoxidation without any loss of catalytic performance.     

Second-harmonic spectroscopy of surface immobilized gold nanospheres above a gold surface supported by self-assembled monolayers

We have investigated linear and nonlinear optical properties of surface immobilized gold nanospheres (SIGNs) above a gold surface with a gap distance of a few nanometers. The nanogap was supported by amine or merocyanine terminated self-assembled monolayers (SAMs) of alkanethiolates. A large second-harmonic generation (SHG) was observed from the SIGN systems at localized surface plasmon resonance condition. The maximum enhancement factor of SHG intensity was found to be 3 x 10(5) for the SIGN system of nanospheres 100 nm in diameter with a gap distance of 0.8 nm. The corresponding susceptibility was estimated to be chi((2))=750 pmV (1.8 x 10(-6) esu). In the SIGN system supported with the merocyanine terminated SAMs, the SHG response was also resonant to the merocyanine in the nanogap. It was found that the SHG response of the SIGN systems is strongly frequency dependent. This leads us to conclude that the large chi((2)) is caused by enhanced electric fields at the localized surface plasmon resonance condition and is not due to an increase of the surface susceptibility following from the presence of the gold nanospheres. The observed SHG was consistent with the theoretical calculations involving Fresnel correction factors, based on the quasistatic approximation.     

Hydrogen-bonded porous coordination polymers: structural transformation, sorption properties, and particle size from kinetic studies

Three new coordination polymers, [CoCl2(4-pmna)2]n (1), {[Co(NCS)2(4-pmna)2].2Me2CO}n (2 superset 2Me2CO), and {[Co(4-pmna)2(H2O)2](NO3)2.2CH3OH}n (3 superset 2H2O.2MeOH) (4-pmna = N-(pyridin-4-ylmethyl)nicotinamide), have been synthesized and characterized using single-crystal X-ray diffraction. The cobalt(II) atoms are bridged by 4-pmna ligands in all three compounds to form double-stranded one-dimensional "repeated rhomboid-type" chains with rectangular-shaped cavities. In 1, each chain slips and obstructs the neighboring cavities so that there are no guest-incorporated pores. Both 2 superset 2Me2CO and 3 superset 2H2O.2MeOH do not have such a staggered arrangement and have pores that can be filled with a guest molecule. Compound 3 superset 2H2O.2MeOH traps guest molecules with multiple hydrogen bonds and shows a reversible structural rearrangement during adsorption and desorption. The new crystalline compound, 3, is stabilized by forming hydrogen bonds with the amide moieties of the 4-pmna ligands and was characterized using infrared spectroscopy. The clathration enthalpy of the reaction 3 + 2H2O(l) + 2MeOH(l) <==> 3 superset 2H2O.2MeOH (approximately 35 kJ/mol) was estimated from differential scanning calorimetry data by considering the vaporization enthalpies of H2O and MeOH. The desorption process of 3 superset 2H2O.2MeOH --> 3 follows a single zero-order reaction mechanism under isothermal conditions. The activation energy of ca. 100 kJ/mol was obtained by plotting the logarithm of the reaction time for the same reacted fraction versus the reciprocal of the temperature. Moreover, the distribution of the one-dimensional channels in 3 superset 2H2O.2MeOH was estimated using the observation that the reaction rate is directly proportional to the total sectional area.     

Preparation and characterization of conducting trimetallic nickel-dithiolene complexes with bridging tetrathiooxalate ligands

Trimetallic nickel dithiolene complexes with two tetrathiooxalate (tto) ligands were obtained by a reaction monitored by ESI-mass spectrometry followed by HPLC separation and were characterized by elemental or crystal structural analysis, MO calculations, and electrical conductivity measurements.     

Synthesis, structural characterization, and catalytic performance of dititanium-substituted gamma-Keggin silicotungstate

A novel titanium-substituted silicotungstate cluster of [{gamma-SiTi2W10O36(OH)2}2(mu-O)2]8- (1) is synthesized by the introduction of titanium(IV) ions into a divacant lacunary gamma-Keggin-type silicotungstate of [gamma-SiW10O36]8-. This titanium-substituted polyoxometalate, 1, exhibits a dimeric structure. One half of the gamma-Keggin fragment of 1 contains a dinuclear titanium center bridged by two hydroxo groups, and the resulting Ti2(mu-OH)2 core connects to the other Ti2(mu-OH)2 core of the paired gamma-Keggin subunit through Ti-O-Ti linkages. The Ti2(mu-OH)2 core of 1 reacts with MeOH to form the corresponding alkoxo derivative, [{gamma-SiTi2W10O36(OH)(OMe)}2(mu-O)2]8- (2). Two of four hydroxo groups of the Ti2(mu-OH)2 cores in 1 are replaced by methoxo groups to give the Ti2(mu-OH)(mu-OMe) core, and the Ti-O-Ti linkages connecting two gamma-Keggin subunits are maintained in 2. The gamma-Keggin dititanium-substituted silicotungstate 1 catalyzes mono-oxygenation reactions, such as the epoxidation of olefins and sulfoxidation of sulfides with hydrogen peroxide under mild conditions, while the monotitanium-substituted silicotungstate, [alpha-SiTiW11O39]4- (3), and the fully occupied silicododecatungstate, [gamma-SiW12O40]4-, are inactive. The epoxidation with 1 is stereospecific; the configurations around the C=C double bonds of the cis- and trans-olefins are completely retained in the corresponding epoxides. For the competitive epoxidation of cis- and trans-2-octenes, the ratio of the formation rate of cis-2,3-epoxyoctane to that of the trans isomer (R(cis)/R(trans)) is relatively high (21.3) in comparison with those observed for the tungstate catalysts, including [gamma-SiW10O34(H2O)2]4-. The epoxidation of 3-methyl-1-cyclohexene is highly diastereoselective and gives the corresponding epoxide with an anti configuration. The molecular structure of 1 is preserved during the catalysis because the 29Si and 183W NMR spectra of the catalyst recovered after completion of the oxidation are consistent with those of as-prepared compound 1. All these facts suggest the contribution of rigid nonradical oxidants generated on the multinuclear titanium center of 1.