有机-无机杂化配位聚合物{[C12H28N2][(Pb3I8) (DMF)2]•2DMF}n的晶体及电子结构

合成了一种新颖有机-无机杂化配位聚合物{[C₁₂H₂₈N₂] [(Pb₃I₈)(DMF)₂]•2DMF}_n, 并进行了红外、紫外、热重表征, 采用X射线衍射方法确定了晶体结构. 结构解析表明, 整个分子由阳离子(双质子化的N,N'-二丁基哌嗪)及聚阴离子链([(Pb₃I₈)(DMF)₂]_n^2-)组成, 它们之间由静电作用结合在一起形成一维链状配位聚合物. 依据晶体结构数据, 采用Gaussian03程序对产物进行量子化学计算.     

Strategies for hydrogen storage in metal--organic frameworks

Increased attention is being focused on metal-organic frameworks as candidates for hydrogen storage materials. This is a result of their many favorable attributes, such as high porosity, reproducible and facile syntheses, amenability to scale-up, and chemical modification for targeting desired properties. A discussion of several strategies aimed at improving hydrogen uptake in these materials is presented. These strategies include the optimization of pore size and adsorption energy by linker modification, impregnation, catenation, and the inclusion of open metal sites and lighter metals.     

Inorganic-Organic Hybrid Polymers from the Polymerisation of Methacrylate-Substituted Oxotantalum Clusters with Methylmethacrylate: A Thermomechanical and Spectroscopic Study

New inorganic-organic hybrid materials were prepared by free-radical polymerization of methyl methacrylate (MMA) with methacrylate-substituted oxotantalum cluster [Ta₄O₄(OEt)₈(OMc)₄] and their properties evaluated. The cluster was prepared by the reaction of the parent alkoxide with methacrylic acid. Samples of the hybrid materials were produced with Ta-cluster to methyl methacrylate in the ratios of 1:50 and 1:100 and were characterized by thermal and spectroscopic techniques. The glass transition temperatures of the hybrid materials are shifted to higher temperatures than pure PMMA as a result of cross-linking of the polymer by the oxotantalum clusters. The increase in T_g is also observed from the dynamic mechanical analysis (DMA). Evidence of crosslinking between the Ta-cluster and PMMA is obtained from infrared spectroscopic study. Surface studies performed by X-ray photoelectron spectroscopy (XPS) provide information about the atomic concentrations of the surface and indicate tantalum bonded to oxygen.     

Synthesis and characterization of new strontium 4-carboxyphenylphosphonates

Several new strontium 4-carboxyphenylphosphonates, i.e., two modifications of Sr(HOOCC₆H₄PO₃H)₂, SrH(OOCC₆H₄PO₃)·H₂O, Sr₃(OOCC₆H₄PO₃)₂·4H₂O and Sr₃(OOCC₆H₄PO₃)₂·5.7H₂O were prepared and characterized by elemental analysis, thermogravimetry, X-ray powder diffraction and infrared spectroscopy. It was found that the compositions of these compounds depend on the acidity of the reaction medium. In addition, the presented compounds are interconvertible in dependence on pH. The position of the acid hydrogen atom in SrH(OOCC₆H₄PO₃)·H₂O was determined from the IR spectra of the studied compounds.The structure of the β modification of Sr(HOOCC₆H₄PO₃H)₂ was solved from its X-ray powder diffraction pattern using an ab initio method (the FOX program) with subsequent Rietveld refinement in the FULLPROF program. The compound is monoclinic, with the space group P2₁/c (No. 14), a=49.88(2), b=7.867(2), c=5.602(3) Å, β=128.68(2)°, and Z=4. It has a one-dimensional structure with an inorganic part built of SrO₈ distorted tetragonal antiprisms.     

Cobalt Ion Incorporation into Periodic Mesoporous Organosilica Materials Synthesized by Co-condensation of 1,2-Bistrimethoxysilylethane with 3-Glycidoxypropyltriethoxysilane

Bifunctional periodic mesoporous organosilica materials with and without cobalt ion incorporation were synthesized by co-condensation of 1,2-bistrimethoxysilylethane (BTME) with 3-glycidoxypropyltriethoxysilane (GPTS) in the presence of cetyltrimethylammonium bromide. Nitrogen gas adsorption on samples with varying ratios of BTME:GPTS revealed that increasing the amount of GPTS affects pore size, surface area and pore volume as well as shapes of the isotherms and hysteresis loops. The hysteresis loops of the Type IV isotherms obtained for GPTS-modified ethane silica materials (without cobalt ion) change from Type H3 to Type H4 with increasing GPTS content. There is a tendency for pore sizes to change from mesopore to micropore when the amount of GPTS is increased. Isotherms of cobalt ion incorporated GPTS-modified ethane silica materials change from Type IV to Type I with increasing GPTS content. The surface area, pore volume and pore diameter decrease with increasing loading of GPTS as well as after cobalt ion incorporation. Thermogravimetric analysis and differential thermal analysis show that the surfactant is removed by solvent extraction. Cobalt ion incorporation is confirmed by powder X-ray diffraction and Raman spectroscopy.     

Chemical Modification of Silica Gels

Highly porous pure and polyethyleneglycol (PEG)-doped silica gels have been prepared from tetraethyl orthosilicate (TEOS) in ethanol using NH₄OH base-catalysis. Addition of PEG to the SiO₂-system increases the average particle size and most frequent pore diameter of the resultant gels while their total surface area decreases. The viscosity of the sol increases with PEG concentration and passes through a maximum with increasing molecular weight at PEG 200. Results obtained indicate a definite interaction of the polymer with SiO₂ and that this interaction is not as a result of direct formation of Si– O– C linkage, but is more likely to be due to hydrogen bonding between the hydrated PEG and the Si– O– Si network. Structure-process correlations are considered.     

Gas permeation of porous organic/inorganic hybrid membranes

Selective gas permeation of porous organic/inorganic hybrid membranes via sol-gel route and its thermal stability are described. Separation performance of the hybrid membrane was improved compared with porous membranes governed by the Knudsen flow, and gas permeability was still much higher than that through nonporous membranes. Additionally, it was shown that these membranes were applicable at higher temperatures than organic membranes.SEM observation demonstrated that the thin membrane was crack-free. Nitrogen physisorption isotherms showed the pore size was in the range of nanometers. Gas permeability through this membrane including phenyl group was in the range of 10^–8 [cc(STP) cm/(cm² s cmHg)] at 25°C. The ratios of O₂/N₂ and CO₂/N₂ were 1.5 and 6.0, respectively, showing the permeation was not governed by the Knudsen flow. The permeability decreased as the temperature increased. Furthermore, the specific affinity between gas molecules and surface was observed not only in the permeation data of the hybrid membranes but in the physisorption data. These results suggested that the gas permeation through the hybrid membrane was governed by the surface flow mechanism.Thermal analysis indicated that these functional groups were still stable at higher temperatures. The phenyl group especially remained undamaged even at 400°C.     

New and novel organic-inorganic type crystalline ‘polypyrrolel/polyantimonic acid’ composite system: preparation, characterization and analytical applications as a cation-exchange material and Hg(II) ion-selective membrane electrode

A new phase of ‘organic-inorganic’ composite system, polypyrrole polyantimonic acid, prepared by mixing the inorganic precipitate of hydrated antimony oxide with organic conducting polymer i.e., polypyrrole, providing a novel granular form hybrid cation-exchanger suitable for column operation with better chemical and thermal stability, good ion-exchange capacity, reproducibility and selectivity for heavy metals. The physicochemical properties of this material were studied using elemental analyses, AAS, SEM, XRD, FTIR and simultaneous TGA-DTA studies. Ion-exchange capacity, pH-titrations, elution and distribution behavior were also carried out to characterize the material. Distribution studies revealed the cation-exchange material to be highly selective for Hg(II) and its selectivity was performed by achieving some important binary separations like Hg²⁺-Zn²⁺, Hg²⁺-Ni²⁺, Hg²⁺-Cu²⁺, Hg²⁺-Fe³⁺, Hg²⁺-Cd²⁺, Hg²⁺-Mg²⁺ etc. on its column. Using this electroactive composite material, a new heterogeneous precipitate based selective ion-sensitive membrane electrode was fabricated for the determination of Hg(II) ions in solutions. The membrane electrode is mechanically stable, with a quick response time, and can be operated within a wide pH range. The selectivity coefficients for different cations determined by mixed solution method were found to be less than unity The electrode was also found to be satisfactory in electrometric titrations.     

具有可逆热致变色有机-无机杂化铜化合物的合成及表征

在浓盐酸水溶液中，碘化N，N-二甲基-1，5-二氮杂环[3.2.1]辛烷（[3.2.1-Me₂dabco]I₂）和碘化1-氨基-1，4-二氮杂环[2.2.2]辛烷（[2.2.2-NH₂dabco]I）与氯化铜反应得到2种有机-无机杂化铜化合物[3.2.1-Me₂dabco][CuCl₄]（1）和[2.2.2-NH₂dabco][CuCl₄]（2）。X射线单晶结构衍射证实化合物1和2中的无机阴离子是[CuCl₄]^2-四面体。化合物1和2表现出可逆的热致变色现象，随着温度升高，它们的颜色从黄色变为红色，这应该是由[CuCl₄]^2-四面体的变形引起的。