Zn(p-DMABA)~2Cl~2的低热固相合成及其X射线粉末衍射数据

报道了固配化合物Zn(p-DMABA)~2Cl~2(p-DMABA=N,N'-对二甲胺基苯甲醛)的低热固相合成，并用红外光谱、拉曼光谱、荧光光谱、差热热失重分析对产物进行了表征。结果表明p-DMABA是通过羰基氧原子与金属锌离子配位的。用粉末X射线衍射仪惧了衍射数据，并对衍射数据进行了指标化，指标化结果如下：Zn(p-DMABA)~2Cl~2为单斜晶系，空间群为P2~111(4)，晶胞参数：a=1.5897(2)nm,b=0.7560(4)nm,c=1.0373(1)nm,β=95.23(3)°,V=1.241(2)nm^3。     

SrB6的固相合成及其形成机理

稀土、碱土金属硼化物属难熔类金属无氧型化合物,具有高熔点、高强度和化学稳定性高的特点,其中许多还具有特殊的功能性,如低的电子功函数、比电阻恒定、在一定温度范围内热膨胀值为零、不同类型的磁序以及高的中子吸收系数等。这些优越性能决定其在现代技术各种器件组元中有广泛的应用前景。许多国家相继开展了该类材料的研究,其中SrB6及其复合材料用作高温绝缘体、核反应堆的控制棒等已引起多方重视,此外,文献用扫描隧道电子显微镜分析了SrB6的结构与性能,在研究铝合金的变质过程中,发现SrB6能显著缩短有效变质时间。但迄今为止,系统介绍SrB6粉末合成的文章未见报道,本文研究以SrCO3,B4C和活性C粉为原材料,固相合成SrB6粉的工艺,以及不同温度和保温时间对SrB6粉末合成的影响,探讨合成SrB6粉末的最佳工艺,并对其形成机理作了简要介绍。     

混配化合物M(α-AP)2(OAc)2(M=Ni、Zn)的室温固相合成及表征

Mixed coordination compounds M(α-AP)₂(OAc)₂ (M=Ni， Zn) were synthesized individually via solid phase reactions between α-aminopyridine and nickel acetate or zinc acetate at room temperature and were characterized by elemental analysis， IR and X-ray powder diffraction. Zn(α-AP)₂(OAc)₂ was also determined by ¹H NMR， TGA and X-ray single crystal diffraction. The crystal belongs to monoclinic system with space group P2₁/c， a=9.1900(18)?， b=13.900(3)?， c=13.310(3)?， β=92.40(3)°， V=1698.7(6)?³， D_c=1.453g·cm^-3， Z=4， F(000)=768， μ=1.469mm^-1， R₁=0.0376， wR₂=0.1202[I >2σ(I)]. Each zinc(Ⅱ) atom lies at the center of a distorted tetrahedron composed of two oxygen atoms from a pair of monodentate acetate groups and two nitrogen atoms from a pair of pyridine rings.     

四氯合铜酸二乙铵的低热固相合成及其热色性

本文在低热温度下,通过固相反应合成了四氯合铜酸二乙铵。利用XRD、IR等对固相反应产物进行了表征,通过DSC、原位升温Uv Vis等手段研究了产物的热色性,对固相反应发生的可能性进行了讨论。反应过程中不使用溶剂,操作简单,产率远高于液相合成法。1　实验部分1 1　仪器及试剂DSC7功率补偿型差示扫描量热计,美国PE公司生产,Ar气氛,流速25ml/min,扫描速率10℃/min;FTIRIFS 48型红外分光光度计(IR),德国Bruker公司生产(KBr压片),扫描次数16次,分辨率4cm-1,波数范围4000 400cm-1;原位升温紫外 可见分光光度仪附件,专利号:ZL972433…     

[Cu(TO)2(H2O)4](PA)2的制备、结构表征和热分解机理研究

[Cu（TO）2（H2O）4]（PA）2 was prepared by the reaction of aqueous 1,2,4-triazol-5-one （TO） solution with the solution of copper picrate Cu（PA）2 and characterized by elemental analysis, FT IR and X-ray powder diffraction analysis. The title complex has been studied by means of TG-DTG and DSC under conditions of linear temperature increase. The thermal decomposition residues were examined by FT IR analysis. Thermal decomposition mechanism of the title complex was proposed. In the temperature range of 30-680 ℃, the thermal decomposition process was composed of four major stages. The first stage was an endothermic process with the loss of four coordination water molecules. Since the dehydration product was unstable, when it was heated, it would be decomposed much more easily. The second stage was composed of an acute endothermic process and a continued strong exothermic process and the main decomposed residues were CuCO3, Cu（NCO）2 and polymers during this stage. The third stage was a sharp exothermic process, which resulted from the decomposition of the polymer. After the forth stage, the final decomposed residues were certainly copper oxide. The Arrhenius parameters have been also studied on the dehydration process and the first-step exothermic decomposition of [Cu（TO）2（H2O）4]（PA）2 using Kissinger＇s method and Ozawa-Doyle＇s method. The results using both methods were consistent with each other. The Arrhenius equation can be expressed as in k=24.0-179.8 × 10^3/RT for the dehydration process and in k= 16.7-206.0 × 10^3/RT for the first-step exothermic decomposition, on the basis of the average of Ea and In A through the two methods.     

稀土三元配合物的低热固相合成、表征及抑菌活性研究

首次在室温条件下通过固相反应制得了镧稀土水杨酸8-羟基喹啉三元配合物La(Hsal)2(hq)(hq=C9H6NO^-;Hsal^-=C7H5COO^-)。采用元素分析、红外光谱、X射线粉末衍射、热重-差热分析等手段对配合物进行了表征。同时还初步分析了固相反应的机理。抑菌实验表明该配合物对大肠杆菌、金黄色葡萄球菌、白色念珠菌、芽孢杆菌都有很好的抑菌效果。     

三元混配化合物［Cu(8-Q)2(phen)］·H2O及［Cu(NCS)2(phen)2］·H2O的固相合成

用室温固相反应合成了［Cu(8-Q)₂(phen)］·H₂O及［Cu(NCS)₂(phen)₂］·H₂O两个三元混配化合物。室温下［Cu(Ac)₂(H₂O)］与邻菲啉固体几乎不发生反应,但加入第二配体8-羟基喹啉及KSCN,反应几乎立即发生。XRD、IR谱及元素分析结果表明：第二配体的加入并不仅仅促进［Cu(Ac)₂(H₂     

SnO2 /MWCNTs纳米复合材料的低热固相制备及其超电容特性研究

采用十二烷基三甲基溴化铵(DTAB)辅助固相法制备SnO2/MWCNTs纳米复合材料,X射线衍射(XRD)、透射电镜(TEM)测试表明,SnO2纳米颗粒均匀包裹在MWCNTs表面.循环伏安和恒流充放电测试表明,与SnO2颗粒和纯MWCNTs相比,SnO2/MWCNTs纳米复合材料在1.0 mol·L-1 Na2SO4电解液中的电化学电容性质得到明显改善.当SnO2质量分数为11%时,在电流密度0.2 A·g-1下,SnO2的电容值最大可达217.3 F·g-1.     

层状LiMnO2的固相合成及电化学性能

以Mn₂O₃和氢氧化锂为原料，通过焙烧合成出o-LiMnO₂。用X射线衍射和扫描电镜对不同温度下合成的粉末样品进行了表征，并研究了材料的电化学性能。通过对不同温度条件下烧结样品的晶胞参数、布拉格(110)晶面峰半高宽及电化学性能研究发现：600 ℃下合成样品的半高宽最大，堆垛层错率高，同时电化学性能也最好，首次放电容量达到156 mAh·g^-1，20次循环后仍保持在140 mAh·g^-1以上。中高温固相合成的o-LiMnO₂材料，在晶粒范围大小相近时，材料电化学性能与材料堆垛层错率相关。     

纳米Bi~2O~3微粒的固相合成及其电化学性能的研究

用室温和低温固相反应法,采用两种反应途径合成了纳米Bi~2O~3微粒,并用XRD,TEM,CV及恒流充放实验对其性能进行了研究。     

低热固相反应制备ni0.6cu0.2zn0.2fe2o4纳米晶铁氧体

低热固相反应;溶胶凝胶;nicuzn铁氧体     

一种新的配位聚合物[Cd(SCN)2(POM)2]n的合成和晶体结构(英)

The one-dimensional chain self-assembled coordination polymer, [Cd(SCN)₂(POM)₂]_n(where POM is 3-methyl-4-nitropyridine-N-oxide), was synthesized and characterized. The crystal data for the title coordination polymer: monoclinic, space group P2₁/c, a = 1.182 3(1) nm, b = 0.591 1(1) nm, c = 1.419 2(1) nm, β = 102.875(1)°, Z=2, μ = 1.391 mm^-1, final R₁ = 0.062 8, wR₂ = 0.145 2. The coordination polymer exhibits a strong fluorescent emission band at ca. 518 nm. CCDC: 211506.     

Synthesis, structure and magnetic behavior of a new three-dimensional Manganese phosphite-oxalate: [C2N2H10][Mn2(OH2)2(HPO3)2(C2O4)]

A novel manganese phosphite-oxalate, [C₂N₂H₁₀][Mn₂^II(OH₂)₂(HPO₃)₂(C₂O₄)] has been hydothermally synthesized and its structure determined by single-crystal X-ray diffraction. The structure consists of neutral manganese phosphite layers, [Mn(HPO₃)]_∞, formed by MnO₆ octahedra and HPO₃ units, cross-linked by the oxalate moieties. The organic cations occupy the middle of the 8-membered one-dimensional channels. Magnetic studies indicate weak antiferromagnetic interactions between the Mn²⁺ ions.     

Investigation of phase transitions of a pseudo-hexagonal phase of [Rh(NH3)5Cl]2[Re6S8(CN)6]·3H2O during thermal decomposition

A general motif of the crystal structure of [Rh(NH₃)₅Cl]₂[Re₆S₈(CN)₆]·3H₂O is examined, and the cluster anions are found to form a pseudo-hexagonal sublattice. The thermal decomposition of [Rh(NH₃)₅Cl]₂[Re₆S₈(CN)₆]·3H₂O is studied, and it is shown that in helium atmosphere thermolysis occurs through the formation of intermediate amorphous phases. The final product obtained at 1200°C is a disordered single-phase solid solution of Re_0.75Rh_0.25 based on the structure of rhenium. Powder X-ray diffraction data for solid solutions in the system of Rh-Re are surveyed. It is demonstrated that the data for phases prepared by the thermal decomposition of coordination compounds better match the theoretical state diagram than the experimental one. The dependence of atomic volume on the composition of solid solutions of Re_xRh_1−x is derived. Original Russian Text Copyright ? 2007 by S. A. Gromilov, K. V. Yusenko, and E. A. Shusharina __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 48, No.5, pp.957–962, September–October, 2007.     

锂离子电池正极材料LiMn2O4的低热固相合成与性能表征

锂离子电池具有比能量高、环境污染小等优点,广泛应用于手提电话、便携式电脑、摄像机等设备中。其正极材料的研究是锂离子电池的研究重点。层状结构的LiCoO2、LiNiO2和尖晶石结构的LiMn2O4是仅有的三种能在3.5V以上电位可嵌入Li的正极材料[1~3]。目前市售的锂离子电池主要采用LiCoO2作正极材料,但由于Co资源缺乏和价格相对昂贵,而锰资源丰富,价格低廉且无毒,对环境友好,因此世界各国都在大力进行以LiMn2O4为正极材料的锂离子电池的实用化研究。LiMn2O4传统的制备方法是高温固相反应合成法[4~7],但由于Mn的变价多,与Li形成贫Li或…     

三核钼－硫簇合物的低热固相合成及其晶体结构

三核钼－硫配合物Ｍｏ_３Ｓ_７（ｄｔｃ）_３Ｉ·Ｓ_８·２ＣＨ_２Ｃｌ_２（ｄｔｃ＝Ｃ_４Ｈ_８ＮＣＳ_２~－）是由低热固相合成得到的。晶体属单斜晶系，Ｍ_ｒ＝１５００．１９，空间群Ｐ２_１／ｎ，ａ＝１１．８８１（３），ｂ＝１５．５５９（４），ｃ＝２６．１９７（７），β＝９８．５３（２）°，Ｖ＝４７８９Ａ~３，Ｚ＝４，Ｄ_ｃ＝２．０８ｇ／ｃｍ~３，Ｆ（０００）＝２９２０，μ（ＭｏＫα）＝２５．２４ｃｍ~（－１），对于２３９７个Ｉ≥３σ（Ｉ）的独立衍射点，最终偏离因子Ｒ＝０．０６０，Ｒ＝０．０６６。该配合物的基本骨架是［Ｍｏ_３Ｓ_７（ｄｔｃ）_３］~＋，其簇芯为［Ｍｏ_３Ｓ_７］~（４＋）单元，３中Ｍｏ原子组成正三角形平面，Ｍｏ－Ｍｏ的平均键长力２．７２３，Ｍｏ原子平面上的硫原子形成盖帽的μ_３－Ｓ，其Ｍｏ－Ｓ平均键长为２．３８３Ａ，３个Ｓ_２基团分别位于三角形３个棱的外侧，并分别与邻近的两个Ｍｏ原子结合形成１２中Ｍｏ－Ｓ键。与μ_３－Ｓ相对而位于平面另一侧的Ⅰ原子与３个μ_２－Ｓ连结，平均距离为３．２５７Ａ，成键作用较弱。     

Synthesis of nanostructured LiTi2(PO4)3 powder by a Pechini-type polymerizable complex method

The nanostructured NASICON-type LiTi₂(PO₄)₃ (LTP) material has been synthesized by Pechini-type polymerizable complex method. The use of water-soluble ammonium citratoperoxotitanate (IV) metal complex instead of alkoxides as precursor allows to prepare monophase material. Thermal analyses have been carried out on the powder precursor to check the weight loss and synthesis temperature. X-ray powder diffraction analysis (XRD) has been performed on the LTP powder obtained after heating the powder precursor over a temperature range from 550 to 1050 °C for 2 h. By varying the molar ratio of citric acid to metal ion (CA/Ti) and citric acid to ethylene glycol (CA/EG), the grain size of the LTP powder could be modified. The formation of small and well-crystalline grains, in the order of 50-125 nm in size, has been determined from the XRD patterns and confirmed by transmission electron microscopy.     

三核钼－硫簇合物的低热固相合成及其晶体结构

三核钼－硫配合物Ｍｏ_３Ｓ_７（ｄｔｃ）_３Ｉ·Ｓ_８·２ＣＨ_２Ｃｌ_２（ｄｔｃ＝Ｃ_４Ｈ_８ＮＣＳ_２~－）是由低热固相合成得到的。晶体属单斜晶系，Ｍ_ｒ＝１５００．１９，空间群Ｐ２_１／ｎ，ａ＝１１．８８１（３），ｂ＝１５．５５９（４），ｃ＝２６．１９７（７），β＝９８．５３（２）°，Ｖ＝４７８９Ａ~３，Ｚ＝４，Ｄ_ｃ＝２．０８ｇ／ｃｍ~３，Ｆ（０００）＝２９２０，μ（ＭｏＫα）＝２５．２４ｃｍ~（－１），对于２３９７个Ｉ≥３σ（Ｉ）的独立衍射点，最终偏离因子Ｒ＝０．０６０，Ｒ＝０．０６６。该配合物的基本骨架是［Ｍｏ_３Ｓ_７（ｄｔｃ）_３］~＋，其簇芯为［Ｍｏ_３Ｓ_７］~（４＋）单元，３中Ｍｏ原子组成正三角形平面，Ｍｏ－Ｍｏ的平均键长力２．７２３，Ｍｏ原子平面上的硫原子形成盖帽的μ_３－Ｓ，其Ｍｏ－Ｓ平均键长为２．３８３Ａ，３个Ｓ_２基团分别位于三角形３个棱的外侧，并分别与邻近的两个Ｍｏ原子结合形成１２中Ｍｏ－Ｓ键。与μ_３－Ｓ相对而位于平面另一侧的Ⅰ原子与３个μ_２－Ｓ连结，平均距离为３．２５７Ａ，成键作用较弱。     

Hydrothermal synthesis and crystal structure of Cs6[(UO2)4(W5O21)(OH)2(H2O)2]: a new polar uranyl tungstate

The hydrothermal reaction of UO₃, WO₃, and CsIO₄ leads to the formation of Cs₆[(UO₂)₄(W₅O₂₁)(OH)₂(H₂O)₂] and UO₂(IO₃)₂(H₂O). Cs₆[(UO₂)₄(W₅O₂₁)(OH)₂(H₂O)₂] is the first example of a hydrothermally synthesized uranyl tungstate. It's structure has been determined by single-crystal X-ray diffraction. Crystallographic data: tetragonal, space group I4 cm, , , Z=4, MoKα, , R(F)=2.84% for 135 parameters with 2300 reflections with I>2σ(I). The structure is comprised of two-dimensional anionic layers that are separated by Cs⁺ cations. The coordination polyhedra found in the novel layers consist of UO₇ pentagonal bipyramids, WO₆ distorted octahedra, and WO₅ square pyramids. The UO₇ polyhedra are formed from the binding of five equatorial oxygen atoms around a central uranyl, UO₂²⁺, unit. Both bridging and terminal oxo ligands are employed in forming the WO₅ square pyramidal units, while oxo, hydroxo, and aqua ligands are found in the WO₆ distorted octahedra. In the layers, four (UO₂)O₅ polyhedra corner share with equatorial oxygen atoms to form a U₄O₂₄ tetramer entity with a square site in the center; a tungsten atom populates the center of each of these sites to form a U₄WO₂₅ pentamer unit. The pentamer units that result are connected in two dimensions by edge-shared dimers of WO₆ octahedra to form the two-dimensional [(UO₂)₄(W₅O₂₁)(OH)₂(H₂O)₂]^6- layers. The lack of inversion symmetry in Cs₆[(UO₂)₄(W₅O₂₁)(OH)₂(H₂O)₂] can be directly contributed to the WO₅ square pyramids found in the pentamer units. In the structure, all of these polar polyhedra align their terminal oxygens in the same orientation, along the c axis, thus resulting in a polar compound.     

Synthesis of trinuclear silicon-, germanium-, and tin-containing tungsten carbene complexes [(ButO)2(Cl)2W=CH]2EPh2 (E = Si, Ge, or Sn). Crystal structure of [(ButO)2(Cl)2W=CH]2SiPh2 complex

New trinuclear organosilicon, organogermanium, and organotin-containing tungsten carbene complexes Ph₂E[CH=WCl₂(OBu^t)₂]₂ (E = Si, Ge, or Sn) were synthesized by the reaction of the trinuclear carbyne complexes Ph₂E[C≡W(OBu^t)₃]₂ with HCl. The tin-containing carbene complex is thermally unstable and was identified in solution by ¹H and ¹³C NMR spectroscopy. The silicon-and germanium-tungsten carbene complexes were isolated in high yields as individual crystals and were characterized by elemental analysis, IR spectroscopy, and ¹H and ¹³C NMR spectroscopy. The structure of the silicon-containing complex Ph₂Si[CH=WCl₂(OBu^t)₂]₂ was established by X-ray diffraction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2424–2427, November, 2005.