[Mn(NH2NHCO2C2H5)3](NO3)2的晶体结构和热分解机理

[Mn(ECZ)₃](NO₃)₂ is newly prepared by the aqueous solutions of Mn(NO₃)₂ and ethyl carbazate (ECZ). The crystal structure has been determined by X-ray crystal diffraction analysis. It belongs to monoclinic with space group of P2₁/n. The crystal parameters are: a=1.3974(2) nm, b=0.8796(2) nm, c=3.4322(7) nm, β=91.25(1) °, V= 4.2175(1) nm³, Z=8. Its molecular weight is 491.30. Mn²⁺ is located on the center of the molecular structure. Ethyl carbazate serves as a bidentate ligand which coordinates to the metal cations with its carbonyl oxygen atom and the terminal hydrazine nitrogen atom, forming five-member chelating rings, and three such rings are formed in each molecule. The coordination number of the metal ion is six and the coordination configuration of the central ion is octahedral. Specially, antimer configuration phenomenon is found in the molecule. The complex is further characterized by element analysis and IR measurements. The thermal decomposition mechanism is studied by using TG-DTG and DSC techniques. CCDC: 215675.     

ZrW0.8Mo1.2O8立方相和正交相的微波合成及其表征

Both the cubic and orthorhombic ZrW_0.8Mo_1.2O₈ were prepared by precursor-microwave route. The cubic phase belonged to β-ZrW₂O₈ structure type and the orthorhombic phase was refined with the structural model of LT- ZrMo₂O₈ by the Rietveld method. The orthorhombic phase belonged to Pmn2₁ space group and the cell parameters were a_o=0.597 1(9) nm, b_o=0.730 6(1) nm, c_o=0.912 7(1) nm, R_p%=9.37; wR_p%=11.81. The TEM images were also given. The comparison was made between precursor-heated and precursor-microwave routes. Metastable polymorphic phase was favorably formed by the latter method.     

配合物[Tb(p-ClBA)3(phen)]2的结构和性能

Terbium p-chlorobenzoate complex with 1,10-phenanthroline, [Tb(p-ClBA)₃(phen)]₂(1) has been obtained in the ethanol solution, where p-ClBA=p-chlorobenzoate and phen=1,10-phenanthroline. It crystallizes in the triclinic system, space group P1, a=1.008 1(2) nm, b=1.185 7(2) nm, c=1.431 1(3) nm, α=110.826(4)°, β=96.436(4)°, γ=101.737(4)°, Z=2. The two Tb(III) ions are linked by four carboxylate groups through their bidentate bridging modes, forming a dimeric unit with crystallographic inversion center. Each terbium ion has an eight-coordinate geometry with four of the coordination sites occupied by four oxygen atoms from the four bridging carboxylates, respectively, two oxygen atoms from bidentate carboxylate, and the remaining positions occupied by two nitrogen atoms from a 1,10-phenanthroline molecule. The Tb(III) ion adopt a distorted square antiprism coordination geometry. The excitation and luminescence data observed at room temperature show that the title complex emits very intensive green fluorescence under ultraviolet light. The result of thermal analysis indicates the complex [Tb(p-ClBA)₃(phen)]₂ is quite stable to heat. CCDC: 221921.     

异核配合物K2[Co(Dipc)2]·7H2O的合成、性质、结构和热分解动力学研究

A heteronuclear compound, K₂[Co(Dipc)₂]·7H₂O (Dipc=pyridine-2,6-dicarboxylic acid) has been synthe- sized and characterized by IR, elemental analysis, and X-ray diffraction. Crystal data: orthorhombic system with space group Pnna and unite cell parameters: a=2.0645(3)nm, b=1.3484(2)nm, c=0.8204(1)nm; V=2.2838(6)nm³, Z=4, D_cald=1.726 g·cm^-3, μ=1.193 mm^-1, F(000)=1212, Gof=1.045, Δρ=339～-348 e·nm^-3, the final R is 0.0295. In the molecule of the complex, Co(Ⅱ) ion is six-coordinate to form a dis-torted octahedron. The N atom and the carboxyl group of pyridine-2,6-dicarboxylic acid are coordinated with the central ions. One of the carboxyl groups of the pyridine-2,6-dicarboxylic acid connect K(Ⅰ) and Co(Ⅱ). The com- pound possesses approximate C₂ symmetry. The compounds form a three-dimensional network of infinite length connection with crystal waters, potassium ions and hydrogen bonds. The result of kinetics of thermal decomposition indicated that the compound decomposition takes place in two steps. CCDC: 207078.     

一维链状铽配位聚合物{[Tb(p-MBA)2(H2O)2]2·(4，4′-bipy)2}n的合成、晶体结构及荧光分析

A novel one-dimensional chain coordination polymer of terbium(Ⅲ) with p-methylbenzoic acid, 2,2′-bi-pyridine and 4,4′-bipyridine has been synthesized and characterized. The crystal data of this complex C₃₉H₃₇N₃O₈Tb are as follows: monoclinic system, space group P2₁/n, a=0.974 01(10) nm, b=2.605 8(3) nm, c=1.457 77(14) nm, β=96.108(2)°, V=3.678 9(6) nm³, D_c=1.507 g·cm^-3, M_r=834.64, Z=4, μ(Mo Kα)=1.978 mm^-1, F(000)=1 684, R₁=0.032 4, wR₂=0.063 4. The crystal structure of the complex shows that the terbium(Ⅲ) ion is coordinated with eight oxygen atoms, six from five p-methylbenzoic acid molecules and two from two water molecules, respectively, forming the distorted tetraprism geometry. The luminescent property of the complex is also studied. CCDC: 619216.     

一维链状柔性羧酸镉配位聚合物[Cd(p-BDOA)·2H2O]n的合成、结构与性质研究(英)

A novel 1-D Cd(Ⅱ) coordination polymer, [Cd(p-BDOA)·2H₂O]_n(I) ( p-BDOA^2-=benzene-1,4-dioxyacetate dianion) has been synthesized and characterized by elemental analysis, IR, PL, TG and X-ray single crystal diffraction. The Crystal crystallizes in monoclinic system, the space group is C2/c, with the crystal cell parameters a=1.175 1(1) nm, b=0.551 0(1) nm, c=1.827 7(2) nm, β=96.14(2)°, and V=1.176 6(3) nm^3,, M_r=372.60, R=0.045 9, wR=0.127 9. The Cd(Ⅱ) ion has a trigonal prism coordination configuration that defined by four carboxyl O atoms from two different p-BDOA^2- ligands and two water molecules. Adjacent Cd(Ⅱ) ions are linked by carboxylate groups with the bidentate coordination mode, giving rise to a chain structure with the adjacent Cd…Cd distance of 1.526 3(5) nm. Furthermore, such chains are linked by hydrogen bonds to form supramolecular network. The results of PL and TG show that the complex exhibits intense fluorescent emissions and its chain skeleton is thermally stable up to 419 K. CCDC: 220443.     

[(NH2CH2CH2NH3)2WⅥO2(NHC6H4NH)2]2(NH2CH2CH2NH2)·H2O配合物的合成与晶体结构

Cis-dioxo-tungsten(Ⅵ) complex, (NH₂CH₂CH₂NH₂)[(NH₂CH₂CH₂NH₃)₂W^ⅥO₂(NHC₆H₄NH)₂]₂·H₂O is synthesized at room temperature by the reaction of sodium tungstate with o-phenylenediamine. The crystal structure of complex was determined by X-ray diffraction structural analysis. The results show that complex belongs to monoclinic system with space group P2₁/ c, a=0.712 8(2) nm, b=3.081 1(10) nm, c=0.981 9(3) nm, β=102.615(4)°, V=2.104 4(11) nm³, Z=2, μ=55.26 cm^-1, F(000)=1 176. Compared the complex with its analogous biomimetic complexes of the cofactor of molybdoenzymes and tungstoenzymses, it is found that the variance of the coordination atoms and the metal ions center have no influence on the coordination feature, and exhibits distored octahedral coordination with cis-dioxo o-phenylenediamine. CCDC: 252834.     

壳聚糖/Pb(Ⅱ)模板壳聚糖膜与Pb(Ⅱ)螯合反应的动力学及机理探讨

Chitosan and chitosan membranes with Pb(Ⅱ) ion as template were studied. The adsorption isotherms were correlated by dc/dt=-kcⁿ at the temperature of 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃. By means of linear correlation, the shapes of the isotherm curves were similar to the kinetic function of 2/c^1/2=-kt and the apparent activation energy for with chitosan(123.8 kJ·moL^-1) was larger than that of membrane with Pb(Ⅱ) ion(92.3kJ·moL^-1). The chitosan membrane with Pb(Ⅱ) ion template was better “memory” function. The adsorption mechanism of chitosan with Pb(Ⅱ) was studied by IR and XPS. The results indicated that the nitrogen in -NH₂ and the oxygen in C₃-OH of chitosan were coordination atoms.     

一种新的三维超分子化合物[Ni(H2O)6(fum)]·2(hmt)·4H2O的合成和晶体结构(fum=反丁烯二酸根；hmt=六次甲基四胺)

The synthesis of nickel supramolecular compound with hexamethylenetetramine and fumarate ligands is reported. The compound [Ni(H₂O)₆(fum)]·2(hmt)·4H₂O (1) (fum=fumarate; hmt=hexamethylenetetramine) were characterized by elemental analysis, crystal structure, IR. Compound 1 crystallizes in the triclinic system, space group P1, and with Z=1. Cell parameters: a=0. 934 6(1), b=0.933 8(1), c=0.938 8(2) nm, α=79.46(1)°, β=77.84(1)°, γ=61.29 6(7)°. Every metal ion has a octahedral coordination geometry formed by six oxygen atoms from six water molecules, and the relative independent components [Ni(H₂O)₆]²⁺, fumarate anions, hmt and H₂O molecules are linked together by two kinds of hydrogen bonds (O-H…O, and O-H…N) to form a three-dimensional structure. CCDC: 256355.     

氯化六咪唑合铁四水分子的结构表征和电化学性能研究(英)

The crystal structure of the title compound, [Fe(Im)₆]Cl₂·4H₂O, (Im=imidazole) was determined by X-ray analysis. The crystal structure consists of Fe(Im)₆²⁺ cation, two Cl^- anions and four non-coordinated water molecules. It crystallizes in the triclinic system, space group P1, with lattice parameters a=0.879 7(2) nm, b=0.906 8(2) nm, c=1.058 1(2) nm, α=75.35(3)°, β=83.20(3)°, γ=61.85(3)°, and Z=1; The Fe(Ⅱ) ion assumes centrosymmetric octahedron geometry with the FeN₆ core. Six imidazole molecules are coordinated to each iron(Ⅱ) ion through its tertiary nitrogen atom. The bond distances of Fe-N are in range of 0.212 8(1) nm to 0.220 4(1) nm. In the solid state, [Fe(Im)₆]²⁺, H₂O molecules and chlorine anions form three dimensional hydrogen bonds network which stabilized the crystal structure. Elemental analysis and electronic spectrum are in agreement with the structural data. The thermal gravity (TG) data indicate that thermal decomposition of the title compound takes place in five steps. In these cases, the residue may be Fe. From the cyclic voltammogram measurement in EtOH/H₂O, we know that electrode reaction was a quasi-reversible process. CCDC: 215335.     

Die Phase La2U2N5

In the system U–La–N a new phase of composition La₂U₂N₅ was observed. The differaction pattern of this phase can be indexed with a tetragonal unit cell:a=8.43 Å,c=8.50 Å andc/a=1.008. The pseudocubic sub-cell withaca/2 is closely related to the CsCl-type.

Auszug aus der von der Technisch-Naturwissenschaftlichen Fakuktät der TU Wien approbierten Diplomarbait des Herrn Dipl.-Ing.J. Waldhart.     

2-Azetidinones from 3-aminopropanoic acids and thePh 3P/CCl4(CBr4) orPh 3P/Br2(I2) condensation systems

The title complexes are used as intramolecular cyclization agents to yield under mild conditions and average to good yields 2-azetidinones from variously substituted 3-aminopropanoic acids. The reaction is found to proceed in all examined cases stereospecifically, with one exception. No marked difference with respect to yields and stereospecificity is noted among the four condensation systems.

---

2-Azetidinone aus 3-Aminopropansäuren und Ph₃ P/CCl ₄(CBr ₄) oder Ph₃ P/Br ₂(I ₂) als Kondensationsmittel

Zusammenfassung Die im Titel angegebenen Systeme wurden als Cyclisationsreagentien eingesetzt, um aus substituierten 3-Aminopropansäuren 2-Azetidinone unter milden Bedingungen und mit durchschnittlichen bis guten Ausbeuten darzustellen. Mit einer Ausnahme läuft die Reaktion stereospezifisch. Bei den vier untersuchten Systemen wurde kein beträchtlicher Unterschied in bezug auf Ausbeute und Stereospezifität festgestellt.

     

Comparative study of structural stability in [NH4−n (CH3) n ]2HgCl4 and in related compounds

The structural instability of the [NH_4−n (CH₃) _n ]₂HgCl₄ group has been investigated. Consideration of different crystals of this family shows that the H-bonds, obviously, hinder the appearance of incommensurate modulation. The dependence of phase transition sequence on the sizes of cation and anion may be obtained only for crystals with simple cation. The appearance of H-bonds complicates the situation and, leads to gradual disappearance of IC phase in the A₂BX₄ family.     

用于NO_x低温下吸附还原的CoO_x/CeO_2二元氧化物的制备

研究了以多孔二氧化硅微球和活性炭为载体制备NOx吸附/还原催化剂的方法,摸索了最佳Ce/Co物质的量的比例。采用低温氮吸附方法测定了样品的BET比表面和孔容,利用XRD方法表征了样品中所掺杂的金属元素的晶型。研究发现:当nCe/nCo=75/25时,材料获得最佳NOx吸附能力,当以多孔二氧化硅微球作载体时,材料对于NOx的吸附主要来自CoOx和CeO2的二元氧化物;当以活性炭作为载体时,活性炭参与了NOx的吸附,因此其吸附容量大大提高。对NOx的吸附机理进行了探讨,并研究了样品的NH3还原性质。     

Die Kristallstruktur von Ca2As2O7

The structure of Ca₂As₂O₇ (a ₀=7.05,b ₀=9.30,c ₀=4.89 Å; =101.3°; space groupC2/m-C _2h ³ ;Z=2) has been solved from 465 independent X-ray intensities collected on aWeissenberg-type diffractometer up to anR-factor of 2.4% for all intensities. The structure of Ca₂As₂O₇ represents a further Thortveitite structure type.

     

LixNi0.8-yCo0.2ZnyOp的合成及电化学性能研究

A series of single-phase Li_xNi_0.8-yCo_0.2Zn_yO_p(0.96 ≤x≤ 1.10， 0 ≤y≤ 0.05， 2 ≤p≤ 2(1+y) ) (different in the y values) were synthesized by a two-step solid state reaction method， in which LiOH·H₂O， Zn-doped spherical Ni(OH)₂ and Co₂O₃ were used as the precursors. The ICP-AES analyses proved that the Zn-doped compounds synthesized had the nonstoichiometric form. The results of the XRD， SEM identified that the uniform particles of the as-prepared materials having a good layered structure were fine， narrowly distributed and well crystallized. The electrochemical performance test was carried out and the results showed that the as-prepared Zn-doped materials had not only a high capacity， but also a better cycling stability characterization than the un-doped one. The Li_1.06Ni_0.75Co_0.22Zn_0.03O_2.03 material has an initial reversible capacity as high as 160.5mAh·g^-1; and a first discharge efficiency 89.2%， and exhibits satisfactory cyclic stability with 90% retainable capacity after 50 cycles.     

Sodium and silver phosphate glasses doped with chlorides of Fe,Mn and Zn

A number of samples of sodium and silver phosphate glasses doped with various compositions of some transition metals viz. iron, manganese and zinc chlorides alongwith undoped samples of sodium and silver phosphate glasses were synthesized and characterized by X-ray diffraction, IR spectral, electrical conductivity and differential scanning calorimetry (DSC). The glass transition temperature (T _g) and crystallization temperature (T _c) values obtained from DSC curves were found to increase with increasing concentration of the dopant Fe/Mn/Zn chlorides in both sodium and silver phosphate glasses and the following sequence is observed: T _g(–FeCl₃)>T _g(–MnCl₂)>T _g(–ZnCl₂) T _c(–FeCl₃)>T _c(–MnCl₂)>T _c(–ZnCl₂) The increase in T _g and T _c values indicate enhanced chemical durability of the doped glasses. The electrical conductivity values and the results of FTIR spectral studies have been correlated with the structural changes in the glass matrix by the addition of different transition metal cations as dopants.     

Na3Fe2S4, ein Thioferrat mit gemischt valenter sk∞/1[FeS2]-Kette

Na₃Fe₂S₄ has been prepared from Na₂S, S and Fe. It crystallizes in space group Pnma,a=6.6333 (5) Å,b=10.675 (1) Å,c=10.677 (2) Å,Z=4. The crystal structure, as determined from single crystal four-circle diffractometer data (R=2.8%), consists of sk/1[FeS₂]-chains formed by slightly distorted edge sharing [FeS₄]-tetrahedra, the iron atoms having a formal valency of +2.5. The sodium ions are approximately octahedrally coordinated. Exposed to air, Na₃Fe₂S₄ readily takes up water to form a hydrate by a pertially topochemical reaction.

     

CCl2(A 1B 1,a3B1)自由基被烷烃类分子猝灭动力学

用放电 LIF实验装置,对CCl4/Ar混合气体放电产生CCl2自由基,再用541.52 nm激光将电子基态CCl2激励到激发态A 1B1(0,4,0)振动能级上,通过检测激发态CCl2时间分辨荧光信号,测得室温下CCl2(A 1B1)被烷烃类分子猝灭的实验结果,用我们提出的三能级模型分析处理实验数据,获得CCl2(A 1B1)态和CCl2(a 3B1)态的碰撞猝灭速率常数kA和ka值.     

CCl2自由基被无机小分子猝灭的速率常数

对CCl4/Ar混合气体脉冲直流高压放电产生CCl2自由基,用541.52 nm激光将电子基态CCl2激励到A 1B1(0,4,0)振动能级上. 通过检测激发态CCl2时间分辨荧光信号,测得室温下CCl2(A 1B1和a 3B1)被O2、N2、NO、 CO2、 CS2、H2O、SO2,和SF6分子猝灭的实验结果.用我们提出的三能级模型分析处理实验数据,获得了CCl2(A 1B1)态和CCl2(a 3B1)态的碰撞猝灭速率常数kA和ka值.