Hydrothermal synthesis,crystal structure and physical properties of {[Gd(H2O)4(μ2-C6NO2H5)2Gd(H2O)4](μ3-C6NO2H4)2(ZnCl3)2} · 2H2O · 2Cl

A bimetallic 4f–3d tetranuclear complex {[Gd(H₂O)₄(μ₂-C₆NO₂H₅)₂Gd(H₂O)₄](μ₃-C₆NO₂H₄)₂(ZnCl₃)₂} · 2H₂O · 2Cl (1) has been synthesized via hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction. Complex 1 is characterized by a tetranuclear Gd₂Zn₂ structure with the gadolinium and zinc atoms interconnected by isonicotinic acid ligands. The tetranuclear species of {[Gd(H₂O)₄(μ₂-C₆NO₂H₅)₂Gd(H₂O)₄](μ₃-C₆NO₂H₄)₂(ZnCl₃)₂} link to isolated chlorine ions and water molecules via π?π interactions and hydrogen bonds to yield a 3-D supramolecular framework. Photoluminescent investigation reveals that the title complex displays an emission in ultraviolet region. The solid-state diffuse reflectance spectra of 1 reveal the presence of a sharp optical gap of 3.66 eV.     

CaC2O4—H2C2O4—H2O体系相平衡研究

测量了25 C时CaC_2O_4-H_2C_2O_4-H_2O三元系的固液平衡数据,实验数据用Pitzer模型进行了关联。     

Synthesis and crystal structure of [nBu4N][Er(pic)4] · 5.5H2O: a new infrared emitter

The new erbium(III) complex of picolinic acid (Hpic), [ⁿBu₄N][Er(pic)₄] · 5.5H₂O, was synthesized and the crystal structure determined by single-crystal X-ray diffraction. The compound was further characterized using IR, Raman, ¹H NMR and elemental analysis. The picolinate ligands (pic⁻) are coordinated through N,O-chelation to the erbium cations, as shown by X-ray diffraction and spectroscopic results, leading to an eight coordinate complex. Photoluminescence measurements were performed for this compound which exhibits infrared emission.     

(NH4)2C2O4·H2O和NH4HC2O4·0.5H2O 单晶的培养研究

利用六次甲基四胺缓慢水解产生的NH3和草酸反应,扩散法培养出(NH4)2C2O4·H2O和NH4HC2O4·0.5H2O两种单晶.     

Synthesis,crystal structure,and thermal stability of a novel 3D cadmium carboxyphosphonate containing left-hand helical chains Cd3Cl2[(O3PCH2–N(H)C5H9–COO)2(H2O)2] · 4H2O

A novel 3D cadmium carboxyphosphonate containing left-hand helical chains, Cd₃Cl₂[(O₃PCH₂–N(H)C₅H₉–COO)₂(H₂O)₂] · 4H₂O 1 has been synthesized by hydrothermal reaction at 120 °C and structurally characterized by single-crystal X-ray diffraction as well as with infrared spectroscopy, elemental analysis and thermogravimetric analysis. In compound 1, the hexanuclear clusters based on Cd(1)O₄Cl₂, Cd(2)O₄Cl₂, Cd(3)O₆ and CPO₃ polyhedra are interconnected through carboxyphosphonate ligands to form a 3D open-framework structure with channel system. The result of connections in this manner is the formation of 20- and 30-atom rings that are parallel to one another and run in the a-axis direction. It is interesting that a type of left-hand helical chain is formed by HL^2? ligands bridging Cd₃ ions running along the b-axis.     

A novel uranyl complex UO2(tci)(C3H5N2) · H2O: Synthesis,crystal structure and characterization

Reaction of uranium oxynitrate hexahydrate with tris(2-carboxyethyl)isocyanurate (tciH₃) in acidic aqueous solution (pH ～4–5) yields the compound UO₂(tci)(C₃H₅N₂) · H₂O. X-ray diffraction shows that the uranyl ion is in a hexagonal bipyramid structure. Uranium ion in the complex is found to be ligated with three chelating COO^? groups at the equatorial plane, two oxygen atoms linking to uranium atom formed the vertical axis. The complex has the layered topology structure in the space. The thermal analysis verifies the component and the structure of the complex.     

A Michael-type reaction between acrylato ions and ethylenediamine coordinated to Ni(II). Synthesis,crystal structure and magnetic properties of [Ni2(EDDP)2(H2O)2] · 2H2O (H2EDDP = ethylenediamine-N,N-dipropionic acid)

The reaction between NiCO₃ · Ni(OH)₂, acrylic acid and ethylenediamine in a 2:4:1 molar ratio affords the binuclear complex, [Ni₂(EDDP)₂(H₂O)₂] · 2H₂O 1. The organic ligand, EDDP^2? (the dianion of the ethylenediamine-N,N-dipropionic acid ligand), results from the addition of one amine group to the carbon–carbon double bonds of two acrylato ions. The crystal structure of 1 consists of neutral centrosymmetric entities, with the nickel ions connected by two carboxylato groups, each one acting as a monoatomic bridge. The intramolecular Ni?Ni distance is 3.212 Å. The metal ions exhibit an octahedral geometry. The cryomagnetic investigation of 1 reveals an antiferromagnetic coupling of the nickel(II) ions (J = ?21.8 cm^?1, H = ?JS_Ni1S_Ni2).     

Mixed solvothermal synthesis and X-ray characterization of a layered copper coordination polymer,Cu(H2O)(1,3-BDC) · H2O (BDC=benzenedicarboxylate)

A novel copper coordination polymer, Cu(H₂O)(1,3-BDC) · H₂O was synthesized by a mixed solvothermal reaction of cupric acetate with 1,3-BDC and characterized by single-crystal X-ray diffraction. This compound crystallizes in a tetragonal space group P4/nmm with cell parameters a=19.1411(5) Å, c=6.7881(2) Å, and Z=8. Its structure contains paddle-wheel-like bi-copper clusters with the pseudo-octahedral centers of Cu(II) ion, Cu₂O₈(H₂O)₂. Every 1,3-BDC fragment links two such clusters to yield a two-dimensional open structure. It was also characterized by infrared spectroscopy, elemental analysis, inductively coupled plasma analysis, differential thermal and thermal gravimetric analyses.     

N2H4/H2O2/CuSO4常压催化氢化SB

首次以水合肼和双氧水的氧化还原反应对两嵌段共聚物SB进行选择性加氢，并着重考察了各种氢化条件对加氢反应的影响，加氢度达到95％。本方法既具有学术上的理论意义，又对光纤材料国产化有重要意义。     

Syndiospecific styrene polymerization by (tert-BuC5H4)TiCl2(O-2,6-iPr2C6H3) – borate catalyst system

(^tBuC₅H₄)TiCl₂(O-2,6-ⁱPr₂C₆H₃) (2) exhibited relatively high catalytic activity for syndiospecific polymerization of styrene at 25 °C if both [PhMe₂NH]B(C₆F₅)₄ and a mixture of AlⁱBu₃/Al(n-C₈H₁₇)₃ were used as the cocatalyst. Effects of both organoaluminum and organoboron compounds were explored, and the effect of cocatalyst was different from that observed in 1-hexene polymerization catalyzed by Cp*TiCl₂(O-2,6-ⁱPr₂C₆H₃) (1). Resultant syndiotactic polystyrene possessed narrow molecular weight distribution under the optimized conditions, and the M_w values were unchanged during the time course.     

H2O2—H2SO4粗化蚀刻液中H2O2浓度的快速测定

根据Ｈ２Ｏ２－Ｈ２ＳＯ４粗化蚀刻液中的Ｈ２Ｏ２与过量Ｆｅ＾２＋离子的定量氧化还原反应，用伏安法测定剩余Ｆｅ＾２＋离子在铂电极上极氧化峰电流，求算Ｈ２Ｏ２的浓度。方法简单，快速，适用于印制电路板生产现场监控。     

Organic–inorganic hybrid oxides: Structure and magnetic properties of [{Cu(terpy)}2Mo6O17(H2O)(O3PCH2NH2CH2PO3)2] · H2O,a bimetallic oxide constructed from novel {Mo6O17(H2O)(O3PCH2NH2CH2PO3)2}4− clusters

The hydrothermal reaction of MoO₃, CuSO₄ · 5H₂O, 2,2′:6′:2″-terpyridine (terpy) and bis-N,N-(methylphosphonic acid) amine (H₂O₃PCH₂NHCH₂PO₃H₂) provided blue crystals of the bimetallic oxide [{Cu(terpy)}₂Mo₆O₁₇(H₂O)(O₃PCH₂NH₂CH₂PO₃)₂] · H₂O (1 · H₂O). The three-dimensional structure of 1 is constructed from {Mo₆O₁₇(H₂O)(O₃PCH₂NH₂CH₂PO₃)₂}⁴⁻ clusters linked through {Cu(terpy)}²⁺ subunits. The cluster consists of three pairs of edge-sharing {MoO₆} octahedra linked through corner-sharing interactions into a {Mo₆O₆} ring. One phosphonate ligand spans the diameter of the ring, bridging four molybdenum sites and leaving at a pendant {PO} group at each terminus. The second diphosphonate ligand exploits one {–PO₃} unit to cap the hexamolybdate ring and bridge all six molybdenum sites while the second {–PO₃} terminus bridges two molybdenum sites, leaving a pendant {PO} unit. Crystal data: C₃₄H₄₅Cu₂Mo₆N₈O₃₅P₄: monoclinic, P2₁/n, a = 11.9431(7) Å, b = 17.382(1) Å, c = 27.524(2) Å, β = 90.429(1)°, V = 5713.7(6) Å³, Z = 4, D_calc = 2.270 g cm⁻³, R₁ = 0.0466.     

SnCl4·5H2O／C催化合成乙酸乙酯

以SnCl4·5H2O/C为催化剂、用乙酸和乙醇为原料,直接酯化合成乙酸乙酯.讨论了醇酸物质的量比、反应温度以及催化剂用量等因素对酯化反应的影响,得出最佳反应条件为催化剂用量为2.5g,乙醇和乙酸的物质的量比为11.5,反应温度为95℃.催化剂重复使用率好,酯的产率高达93.38%.     

[Co(Ⅱ)(H2O)6](C4H4O4)·2C6H12N4·4H2O修饰电极电化学催化谷胱苷肽研究

利用气相沉积法研制了基于TiO2凝胶固定化[Co(H2O)6](C4H4O4).2C6H12N4.4H2O(CoL)修饰电极。研究了该修饰电极对谷胱苷肽(GSH)的催化活性,发现在pH 7.5,0.1 mol/L NaAc-HAc的缓冲溶液中,CoL对电氧化GSH浓度之间有较好的线性关系.线性范围为2×10-6~1×10-4mol/L,检测下限为8×10-7mol/L,相对标准偏差为2.0%(cGSH=5×10-6mol/L,n=6)。应用该法测定生物样品中谷胱苷肽的含量并与紫外分光光度法进行对照,结果一致。     

Effect of steam on the acid strength of H3PW12O40/SiO2 · nH2O and its application in skeletal isomerization of n-butane

The effect of steam on the acid strength of H₃PW₁₂O₄₀ (HPW)/SiO₂ · nH₂O was determined by the Hammett indicators. When the steam content in N₂ was 1.6%, the acidity (H₀ > −13.7) of HPW/SiO₂ · nH₂O could be kept for over 10 h at 300 °C, but for only 2 h when steam was lacking. When it was used as a catalyst for skeletal isomerization of n-butane to isobutane at 300 °C, the HPW/SiO₂ · nH₂O showed stability in the presence of steam (1.6% in feed) better than that without steam, due to a suppression of the loss of crystalline water.     

H2O2—H2SO4系黄铜化学抛光的研究

采用扫描电镜、光反射率法和电化学方法观测了黄铜在Ｈ２Ｏ２－Ｈ２ＳＯ４系化学抛光过程中的表面形貌、表面光亮度、电位时间曲线、电流时间曲线。结果表明，黄铜的化学抛光光包括浸蚀、光亮和过腐蚀三个阶段，同时对黄铜化学抛光机理也进行了探讨。