Darstellung,Konfigurationen und NMR-Daten der Säuren CH3(SR)  CHCOOH (R  C6H5, CH2C6H5, CH2COOH)

Preparation, Configurations and N.M.R. Dates of the Acids CH₃(SR)CHCOOH (R  C₆H₅, CH₂C₆H₅, CH₂COOH) The cis and trans isomers of the acids CH₃(SR)CHCOOH (R  C₆H₅, CH₂C₆H₅, CH₂COOH) were prepared by addition of HSR to CH₃CCCOOH in alkaline water solution and by alkaline hydrolysis of CH₃C(SR)₂CH₂COOC₂H₅ (R  C₆H₅, CH₂C₆H₅, CH₂COOC₂H₅). The oxidation products CH₃C(SO₂R)  CHCOOH (R  C₆H₅, CH₂COOH) were also prepared. The n.m.r. dates of the acids were obtained and some relations between them were discussed.     

[CoI2(C6H4N3CH2CO2C4H2SCO2CH2C6H4N3)], a coordination polymer containing the thiophene-2,5-di(carboxylatomethylenebenzotriazole) bridging ligand: synthesis,structure, redox properties

The title complex was obtained by reacting CoI₂ with thiophene-2,5-di(carboxylatomethylenebenzotriazole) in dichloromethane. The single-crystal X-ray structure analysis of the green material reveals a polymeric chain of CoI₂ units, tetrahedrally coordinated and connected by the 3-nitrogen atoms of the two benzotriazole groups of the multifunctional ligand. The paramagnetic cobalt(II) polymer can be oxidised by hexachloroethane to give the corresponding cationic cobalt(III) complex [CoI₂(C₆H₄N₃CH₂CO₂C₄H₂SCO₂CH₂C₆H₄N₃)(H₂O)₂]⁺ which is diamagnetic and precipitates as the green–yellow chloride salt.     

Ferroelectric and ferroelastic phase transitions in (CH3NH3)3Sb2Br9 crystals

(CH₃NH₃)₃Sb₂Br₉ crystals were studied by pyroelectric method in the temperature range 10 - 200 K. Pyroelectric measurements revealed reversal spontaneous polarization below 141 K along the a-axis. The optical observations showed that MABA possesses ferroelastic domains in all low temperature phases.     

Ferroelectric phase transitions of (CH3NH3)5Bi2Cl11

The spontaneous polarization of (CH₃NH₃)₅Bi₂Cl₁₁ single crystals was measured in the range 80-315 K revealing the existence of a ferro-ferroelectric type transition at 170 K.     

有机锡化合物(o-FC6H4CH2)2SnCl2的合成、表征及晶体结构

利用邻氟苄基氯和锡反应,合成了有机锡化合物(o-FC6H4CH2)2SnCl2。通过元素分析、红外光谱和核磁共振氢谱对其结构进行了表征。用X-射线单晶衍射测定了该化合物的晶体和分子结构。化合物晶体为单斜晶系,空间群C2/c,a=23.794(17),b=4.85(2),c=12.744(9),β=93.880(10)°,V=1467.8(18)3,Z=4,Dc=1.845Mg/m3,μ=2.109mm-1,R=0.0255,wR=0.0738。锡原子呈畸变四面体构型。通过化合物分子间Sn…Cl作用,形成一维链状结构。     

有机锡化合物(C6H5)3SnCl的合成及晶体结构

合成了有机锡化合物(C6H5)3SnCl,通过元素分析、红外光谱和核磁共振氢和锡谱对其结构进行了表征。用X-射线单晶衍射测定了该化合物的晶体和分子结构。化合物晶体为三斜晶系,空间群P,īa=9.740(9),b=18.674(17),c=19.010(17),α=105.513(14)°,β=90.036(14)°,γ=90.258(15)°,V=3 332(5)3,Z=8,Dc=1.537 Mg/m3,μ=1.682mm-1,F(000)=1 520,R=0.045 8,wR=0.103 0。锡原子呈畸变四面体构型。     

NMR Study on (CH 3 ) 2 NH 2 H 2 AsO 4

Proton NMR line width and spin-lattice relaxation time T 1 for the ferroelectric (CH 3 ) 2 NH 2 H 2 AsO 4 have been measured at the temperature range between 77 K and 300 K. The temperature dependence of T 1 is well described by the expressions based on rotation of the methyl group using the value of activation energy E a = 99 meV and elementary correlation time τ0 = 1.5 ×10 -13 sec. Moreover, a sharp dip of T 1 near ferrroelectric phase transition temperature ( T c = 274.5 K) results from the ordering of protons. In addition, the temperature dependence of T 1 deviates from the expression for molecular rotation above around 200 K. It is deduced that the deviation is caused by the suppression of some kind of proton motion.     

Ferroelectric domain structure of (CH3NH3)5Bi2Brll single crystals

Ferroelectric domain structure of (CH₃, NH₃)₅ Bi₂ Br₁₁ single crystals was revealed using nematic liquid crystal decoration and scanning electron microscopy. The domain boundaries observed on the c-surface of the crystal were found to be parallel to the b-orthorhombic axis and this direction was found to be an easy direction of domain growth.     

磁场对(C4H9NH3)2(CH3NH3)Pb2I7钙钛矿发光特性调控的研究

(C₄H₉NH₃)₂(CH₃NH₃)Pb₂I₇是一种Ruddlesden-Popper相钙钛矿材料,具有层状结构,层间通过van der Waals力结合,因此可以通过机械剥离的方法,获得其二维薄层。二维(C₄H₉NH₃)₂(CH₃NH₃)Pb₂I₇内束缚激子会自发复合从而表现出强的荧光,其圆极化率、峰位均受磁场调控。在外磁场中,荧光圆极化率与磁场呈线性关系,激子中电子和空穴之间的朗德因子差Δg约为0.43。束缚激子在磁场中受抗磁效应影响,致使其发光峰随磁场增加而红移。     

Diffusivity of CO2, CH4, C2H6 and N2 in athabasca bitumen

Experimental data for the diffusivity of carbon dioxide, methane, ethane and nitrogen in Athabasca bitumen are presented in the range 25–90°C at 4 and 8 MPa. The diffusivity of these gases has been determined as a function of gas concentration in bitumen using a non‐intrusive experim?ental method. The diffusivity of gas in general is found to increase with temperature and pressure, and is a unimodal function of concentration. A correlation is provided for the average diffusivity of these gases as a function of temperature.     

Highly Active Catalyst from [PdCl2(NH2(CH2)12CH3)2] on NH4ZSM-5

A palladium catalyst highly active for the cyclohexene hydrogenation has been obtained by heterogenisation of [PdCl₂(NH₂(CH₂)₁₂CH₃)₂] on zeolite NH₄ZSM-5. TOF is more than twenty times higher than for the homogeneous catalyst or the activated carbon heterogenised complex. Changes in the electronic state of palladium have been observed by XPS analysis. Palladium reduction is produced upon heterogenisation on the NH₄ZSM-5 zeolite.     

Synthesis,spectroscopic and structural aspects of triphenylantimony(V) complex with internally functionalized acetylferroceneoxime: Crystal and molecular structures of [C5H5FeC5H4C(CH3)NO]2SbPh3 and C5H5FeC5H4C(CH3)NOH

Triorganoantimony(V) complex (C₅H₅FeC₅H₄C(CH₃)NO)₂SbPh₃ (1) has been prepared by the reaction of Ph₃SbCl₂ with acetylferroceneoxime C₅H₅FeC₅H₄C(CH₃)NOH (2) in 1:2 molar ratio in anhydrous toluene. The complexes have been characterized by elemental analyses, IR and NMR (¹H and ¹³C) spectroscopic studies, and biologic activity was measured. And crystal structures of 1, 2 were reported. The coordination geometry around the antimony atom in 1 was slightly distorted trigonal bipyramidal with the carbon atoms of the SbPh₃ unit in equatorial positions and the two oxygen atoms of the oxime group occupying axial positions. The free oxime was clearly hydrogen bonded (H–N 2.10 Å/2.04 Å in 2) to essentially form a dimer.     

CH4, C2H6, and C2H4 Phase Equilibria on SAPO-34 Using the Vacancy Solution Theory

Adsorption data of single, binary, and ternary mixtures of methane, ethane, and ethylene on Silicoalumina-Phosphate molecular Sieve (SAPO-34) were obtained experimentally in the pressure range of 0 to 600 kPa at 303, 313, and 323 K. The adsorbed equilibrium concentration was predicted based on the vacancy solution theory (VST) using excess Gibbs energy (EGE) models of activity coefficients. EGE models were studied comparatively, i.e., the Wilson, Flory Huggins, and NRTL equations. The VSM-model results were compared with the mixture adsorption data. The results revealed higher capability of EGE models against the extended Langmuir equation in predicting adsorption behavior of the so-called gas mixture.     

Dinuclear Rhodium Complexes Containing the Diyne 1,4-C6H4(C≡CH)2 and the Isomeric Bisvinylidene 1,4-C6H4(CH=C:)2 as Bridging Units

The reaction of [RhCl(PiPr₃)₂] ( 1 ) with 1,4-C₆H₄(C≡CH)₂ at 0°C leads almost quantitatively to the formation of the bis(alkyne) complex [(PiPr₃)₂ClRh-(HC≡C₆H₄-C≡CH)RhCl(PiPr₃)₂] (2). At elevated temperatures (THF, 60°C) it rearranges to give the isomeric bis(vinylidene) complex [(PiPr₃)₂ClRh-(=C=CH-C₆H₄-CH=C=)RhCl(PiPr₃)₂] (3). A one-pot synthesis of 3 is also described. Treatment of either 2 or 3 with pyridine affords the bis(alkynyl)dihydrido compound [(PiPr₃)₂(py)Cl(H)Rh(-C≡C-C₆H₄-C≡C-)Rh(H)Cl(py)(PiPr₃)₂] ( 4 ) in which both metal centers are octahedrally coordinated. Whereas the reaction of 2 with NaC₅H₅ produces the complex C_sH₅(PiPr₃)Rh(HC≡C-C₆H₄-C≡CH)Rh(PiPr₃)C₅H₅ ( 7 ), the bis(vinyl-idene) isomer C₅H₅(PiPr₃)Rh(=C=CH-C₆H₄-CH=C=)Rh(PiPr₃)C₅H_s ( 8 ) is obtained from 4 and NaC₅H₅. Electrophiles preferably attack the Rh=C bonds of 8 and thus on protonation with CF₃CO₂H the bis(vinyl) complex C₅H₅(PiPr₃)(CF₃CO₂)-Rh(Z,Z-CH=CH-C₆H₄-CH=CH)Rh(O₂CCF₃)(PiPr₃)C₅H_s ( Z-9 ) is formed. In acetone solution, it rearranges to give the E isomer. Reaction of 8 with sulfur affords the bis(thioketene) complex C₅H₅(PiPr₃)Rh(≡²-C,S; η²-C,S-S=C=CH-C₆H₄-CH=C=S)-Rh(PiPr₃)C₅H₅ ( 12 ), for which only one diastereomer is observed. All attempts to prepare mononuclear rhodium compounds containing the diyne HC≡C-C₆H₄-G≡CH or the isomeric vinylidene: C=CH-C₆H₄-G≡CH as ligand failed.     

Permeation of H2, N2, CH4, C2H6, and C3H8 through asymmetric polyetherimide hollow‐fiber membranes

Permeation properties of pure H₂, N₂, CH₄, C₂H₆, and C₃H₈ through asymmetric polyetherimide (PEI) hollow‐fiber membranes were studied as a function of pressure and temperature. The PEI asymmetric hollow‐fiber membrane was spun from a N‐methyl‐2‐pyrrolidone/ethanol solvent system via a dry‐wet phase‐inversion method, with water as the external coagulant and 50 wt % ethanol in water as the internal coagulant. The prepared asymmetric membrane exhibited sufficiently high selectivity (H₂/N₂ selectivity >50 at 25°C). H₂ permeation through the PEI hollow fiber was dominated by the solution‐diffusion mechanism in the nonporous part. For CH₄ and N₂, the transport mechanism for gas permeation was a combination of Knudsen flow and viscous flow in the porous part and solution diffusion in the nonporous part. In our analysis, operating pressure had little effect on the permeation of H₂, CH₄, and N₂. For C₂H₆ and C₃H₈, however, capillary condensation may have occurred at higher pressures, resulting in an increase in gas permeability. As far as the effect of operating temperature was concerned, H₂ permeability increased greatly with increasing temperature. Meanwhile, a slight permeability increment with increasing temperature was noted for N₂ and CH₄, whereas the permeability of C₂H₆ and C₃H₈ decreased with increasing temperature. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 698–702, 2002     

稀土配合物[Ln(C3H7NO2)-x-(C3H4N2)(H2O)](ClO4)3(Ln=La,-x-=3;Ln=Pr,Nd,Sm,-x-=2)的合成、表征与热分析

合成了稀土高氯酸盐与咪唑、DL α 丙氨酸的4种配合物晶体。经傅里叶变换红外光谱(FTIR)、元素分析和化学分析测定后确定其组成为[Ln(C3H7NO2)x(C3H4N2)(H2O)](ClO4)3(Ln=La,x=3;Ln=Pr,Nd,Sm,x=2)。用差示扫描量热法(DSC)测定了4种配合物的热分解数据,4个配合物开始熔化分解的温度分别为502 5K,532 4K,495 7K,516 7K,配合物有较高的热稳定性。     

Solubility of CO2, CH4, C2H6, C2H4, O2, and N2 in 1-hexyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide: comparison to other ionic liquids

The solubilities of gases in ionic liquids are important in evaluating ionic liquids as solvents for reactions involving permanent gases, as gas storage media, and as solvents for gas separations. Gas solubilities are also important in developing methods to separate solutes from ionic liquid solutions. Here we describe our measurements of the solubilities of CO2, CH4, C2H 6, C2H 4, O2, and N2 in 1-hexyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide and compare these results to our previous investigations. In addition, focus is placed on efforts to tailor ionic liquids to enhance the solubilities of some gases, with particular emphasis on carbon dioxide.     

Polymeric [(R4N){(Me3Sn)2OH}Ni(CN)4]n: from layers (R=nC4H9) to infinite ribbons (R=nC5H11)

In the presence of (nC₅H₁₁)₄N⁺ ions, the earlier described almost planar 14-membered ring system [{(Me₃Sn)₂OH}₂{Ni(CN)₄}₂]²⁻ polymerizes via O–H⋯NC hydrogen bonds to straight, infinite ribbons, while in the presence of the slightly smaller (nC₄H₉)₄N⁺ ion a faintly puckered 2-D framework had been obtained. The dimorphism of the polymeric anion seems to be controlled by weak C–H⋯NC hydrogen bonds.