[Cs(NTO)(H2O)]配合物的合成及表征

本文首次用碳酸铯与NTO直接合成新的Cs-NTO配合物.采用元素分析和化学分析法确定了配合物的组成.用红外光谱法,热分析法和X-ray粉末衍射法进行了物理化学表征.     

3-硝基-1, 2, 4-三唑-5-酮钾配合物的制备、晶体结构和量子化学研究

通过3-硝基-1, 2, 4-三唑-5-酮(NTO)与氢氧化钾水溶液反应,制备了标题配合物, 并用TG, 元素分析, 红外光谱分析对它进行了表征。其结构用单晶分析法测定, 所得晶体学参数为a=0.6408(1),b=0.8218(1), c=1.2626(1)nm, β=100.63ⅲ(1), V=0.6535(1)nm^3,Z=4, Dc=1.892g.cm^-^3, μ=0.785mm^-^1, F(000)=376; 晶体属单斜晶系, 空间群为P21/n, 最终偏离因子R为0.0246。用EHMO计算表明, 标题化合物主要是靠静电引力形成的配合物, 中心原子K与H2O的配位较K与NTO环的结合弱, 预示热解优先脱水。     

3-硝基-1,2,4-三唑-5-酮的锰钴和镍配合物的分子轨道研究

用EHMO方法计算研究3－硝基－1，2，4－三唑－5－酮（NTO）的锰、钴和镍配合物［M（H2O）6］（NTO）2·2H2O（M＝Mn、Co和Ni）的电子结构，通过比较原子上净电荷、原子间重叠布居、前沿分子轨道能级和组成等电子结构参数，阐明了标题物的配位键特征和热解实验．     

Li(NTO)(H2O)2的热分解行为及其结构与性质的关系研究

摘要在水中合成了3-硝基-1,2,4．三唑-5-酮(NTO)的锂盐Li(NTO)(H2O)2,利用DSC,TG／DTG和IR方法研究了其金属配合物的热分解机理,并用Kissinger法、Ozawa法、积分法和微分法对标题配合物进行了非等温动力学研究,得到了热分解反应的动力学参数,确定了热分解第一阶段的动力学方程及配合物的热爆炸临界温度(Tb)为289．33℃．采取RHF／6-31G,DFT-RB3LYP／6-31G方法对标题化合物进行了几何全优化,并对其成键情况、电荷分布和化合物的稳定性进行了分析．     

3-硝基-1, 2, 4-三唑-5-酮锶配合物的制备、晶体结构和热力学 性质研究

通过3-硝基-1,2,4-三唑-5-酮(NTO)与碳酸锶反应,制备了标题配合物,其结构用单晶分析法测定,所得晶体学参数为:a=1.1034(1)nm,b=2.2742(2)nm,c=0.63398(9)nm,β=101.798(13)ⅲ,V=1.5573(4)nm^3,D~c=1.936g.cm^-^3,Z=2,F(000)=912,μ=35.45cm^-^1;晶体属单斜晶系,空间群为P2~1/c,最终偏离因子R为0.0344。通过标题配合物在水中溶解焓的测定,算得其标准生成焓、晶格焓、晶格能和标准脱水焓。     

[Pb(NTO)~2(H~2O)]的制备, 分子结构和热分解机理的研究

通过3-硝基-1, 2, 4-三唑-5-酮(NTO)的钠盐水溶液与硝酸铅水溶液反应, 制备了标题配合物, 并用TG-DTG、元素分析、13^C NMR分析和红外光谱对它进行了表征。其结构用单晶分析法测定, 所得晶体学参数为: a=0.7284(2), b=1.2166(3), c=1.2310(3)nm, β=90.36(2)°, V=1.0908(4)nm^3, Z=4, D~c=2.96g.cm^-3,μ=156.40cm^-1, F(000)=888; 晶体属单斜晶系, 空间群为P2/n, 最终偏离因子R为0.0667。根据TG-DTG和FT-IR技术得到的分析结果, 提出了线性升温条件下标题配合物的热分解机理。     

Schiff碱,咪唑金属配合物的合成与抗癌活性

报道一类新的Ｓｃｈｉｆｆ碱和咪唑的混合型金属配合物，即水杨醛缩甘氨酸，咪唑金属配合物和２，４－二羟基苯甲醛缩丙氨酸，咪唑金属配合物的合成，用溴化乙锭荧光分析法研究了这类配合物与ＤＮＡ的相互作用，其中镍配合物与ＤＮＡ的作用明显。     

3-硝基-1，2，4-三唑-5-酮的铜配合物的量子化学研究

运用EHMO方法对3-硝基-1，2，4-三唑-5-酮(NTO)的铜配合物［Cu(NTO)₂(H₂O)₂］·2H₂O的电子结构进行了计算研究。联系前线轨道能级和电荷分布对体系的稳定性和热解机理作了讨论。     

{[Cd(NTO)_2(CHZ)]·2H_2O}_n的合成、分子结构和热分解机理

通过3-硝基-1,2,4-三唑-5-酮(NTO)镉与碳酰肼(NH2NHCONHNH2,CHZ)反应制备出了新型配合物狖犤Cd(NTO)2(CHZ)犦·2H2O狚n,研究了其分子结构和热分解机理。该配合物的晶体属正交晶系,Pbca空间群,晶体学参数:a=0.8623(1)nm,b=1.8259(4)nm,c=1.9997(3)nm,Z=8。晶体结构经全矩阵最小二乘法修正,最终偏离因子R1=0.0517,wR2=0.0655。中心Cd离子为六配位、畸变的八面体构型,NTO-作为二齿配体同时与2个镉离子形成配位键,三齿配体CHZ的2个配位原子与一个镉离子形成五元螯合环、另1个配位原子与第二个镉离子形成配位键,依次无限延伸,形成三维网状结构的配合物。     

{[Cd(NTO)2(CHZ)]·2H2O}n的合成、分子结构和热分解机理

通过3-硝基-1,2,4-三唑-5-酮(NTO)镉与碳酰肼(NH₂NHCONHNH₂,CHZ)反应制备出了新型配合物{[Cd(NTO)₂(CHZ)]·2H₂O}_n,研究了其分子结构和热分解机理。该配合物的晶体属正交晶系,Pbca空间群,晶体学参数:a=0.8623(1)nm,b=1.8259(4)nm,c=1.9997(3)nm     

CsBr与SmBr3在氢溴酸介质中反应的相化学

由于稀碱稀土卤化物特殊的材料性能，正日益受到各国科学家的关注［‘－3］．动年代初，M：y：：提出了下述4种类型卤化物A’RE？X7（1：2型）、AIREyXgta：2型）、AIRE”X6ta：l型）及AgRE”X。（2：l型）的合成方法（A为碱金属）分析Meyer等人的合成方法网；发现其初始反应是     

Pressure-controlled plasticity of Cu(H2O)6(2+) complex and phase transition in Cs2Cu(ZrF6)2*6H2O

The X-band EPR study of a polycrystalline Cs2Cu(ZrF6)2*6H2O demonstrates a feature of plasticity of the Jahn-Teller Cu(H2O)6 complex in the crystal lattice of this compound. The temperature- and pressure-induced evolution of the spectra shows that the copper complex is extremely sensitive to these factors, which due to the ferroelastic properties of the compound studied modify the internal tetragonal and orthorhombic strains acting on the complex. It is supported by the analysis of the temperature dependencies of the principal values of the g-factor under various pressures, indicating that the complex varies its shape adapting it to the varied conditions. A pressure-induced phase transition is discovered.     

An extended chain structure formed by covalently linking polyoxovanadate cages with tetrahedral six rings

The compound Cs10.5[(V16O40)(Si4.5V1.5O10)].3.5H2O is the first example of an extended structure in which a polyoxometallate anion is linked by an extended tetrahedral unit.     

邻甲氧基羰基苄氧基取代杯[4]芳烃衍生物的合成及其性？…

杯芳烃是继冠醚、环糊精之后的第三代主体分子 [1] .据文献 [2 ,3]报道 ,在杯 [4]芳烃下沿酚氧原子上连接乙酸酯得到的四取代衍生物对 Na+ 有很高的选择性 ,核磁与晶体结构研究均证实这是由于羧酸酯的羰基和酚氧基参与了对 Na+ 的配位 ,而且配位基团所形成的包络空间大小与钠离子相匹配 .一般认为 ,随着包络空间改变 ,对金属离子的识别作用会有所变化[4] .但目前对这方面的工作并没有给予更多的重视 .我们发现 ,用 2 -溴甲基苯甲酸甲酯与杯 [4 ]芳烃反应 ,得到了一种新的四取代杯 [4]芳烃衍生物 2 ,萃取研究结果表明 ,该化合物对钾离子有较…     

Reactivity of polyoxoniobates in acidic solution: controllable assembly and disassembly based on niobium-substituted germanotungstates

The reactivity of polyoxoniobates has been studied in acidic solution by grafting niobium onto trivacant Keggin-type germanotungstates. Four niobium-containing compounds were obtained in the course of this study. Cs(6.5)K(0.5)[GeW(9)(NbO(2))(3)O(37)]·6H(2)O (Cs(6.5)K(0.5)-1) synthesized by the reaction of K(7)H[Nb(6)O(19)] and A-α-Na(10)[GeW(9)0(34)] in H(2)O(2) solution is a tris(peroxoniobium)-substituted A-α-GeW(9) derivative. Cs(6.5)K(0.5)[GeW(9)Nb(3)O(40)]·10H(2)O (Cs(6.5)K(0.5)-2) is a peroxo-free compound obtained by eliminating the peroxo groups in 1. Monomers 1 and 2 as precursors can each afford two nanoscale POMs, dimer Cs(5)[H(15)Ge(2)W(18)Nb(8)O(88)]·18H(2)O (Cs(5)-3) and tetramer Cs(8)K(3)H(9)[Ge(4)W(36)Nb(16)O(166)]·27H(2)O (Cs(8)K(3)H(9)-4), through the formation of Nb-O-Nb bridges. Disassembly through the cleavage of Nb-O-Nb bonds from 4 to 2 and 1 was achieved by controlling the pH and by adding H(2)O(2), respectively. The transition from 1 to 2 can be achieved by simply adding H(2)O(2) to a solution of 1. All four compounds were characterized in the solid state by elemental analysis, infrared spectroscopy, thermogravimetry, and single-crystal X-ray diffraction. (183)W NMR analysis proved that the solid-state structures of polyanions 1-4 were retained after dissolution. Disassembly from 4 to 1 and 2 in solution was observed by (183)W NMR spectroscopy. The UV/Vis spectra of 1 at different pH confirmed that it is stable in the pH range of 0.1-14.0 at room temperature.     

Crystal structure of Li2B12H12: a possible intermediate species in the decomposition of LiBH4

The crystal structure of solvent-free Li2B12H12 has been determined by powder X-ray diffraction and confirmed by a combination of neutron vibrational spectroscopy and first-principles calculations. This compound is a possible intermediate in the dehydrogenation of LiBH4, and its structural characterization is crucial for understanding the decomposition and regeneration of LiBH4. Our results reveal that the structure of Li2B12H12 differs from other known alkali-metal (K, Rb, and Cs) derivatives.     

Unexpected ligand substitutions in the cluster core {Re6Se8}: synthesis and structure of the novel cluster compound Cs11(H3O)[Re6Se4(O)4Cl6]3.4H2O

The compound Cs11(H3O)[Re6Se4(O)4Cl6]3.4H2O containing a novel cluster core {Re6Se4(O)4} with ordered ligands, where the 4 positions of one face of a Se4(O)4 cube are occupied exclusively by Se atoms and 4 O atoms lie in the opposite face was synthesized via the interaction of solid Re6Se8Br2 with molten KOH.     

Selective Oxidation of Propane over CsFePVAsMo Heteropoly Compound Catalyst

Both the partially reduced and non-reduced multi-component heteropoly compound catalysts with Keggin structure were prepared and used for the selective oxidation of propane. The catalysts were characterized by IR, H2-TPR, NH3-TPD, SEM and XRD. The addition of Cs increased the selectivity of acrylic acid and acetic acid. The selective oxidation performance was greatly improved with the addition of As. Among all of the tested catalysts, the catalytic performance of the Cs1.8Fe0.16HxPVAs0.4Mo11O40 (non-reduced) was the best and the maximum yield of acrylic acid reached 16.42%.     

Hydrated Cs+-exchanged MFI zeolites: location and population of Cs+ cations and water molecules in hydrated Cs6.6MFI from in and ex situ powder X-ray diffraction data as a function of temperature and other experimental conditions

Extending our previous investigation of dehydrated, Cs-exchanged MFI zeolites (J. Phys. Chem. B 2006, 110, 97-106) to hydrated analogues, we have determined the crystal structures of members of the Cs(6.6)H(0.3)MFI.xH(2)O series, for 0 < x < 28, from synchrotron-radiation powder diffraction data. In the fully hydrated phase, three independent Cs(+) cations and six water molecules are identified in difference Fourier maps. The populations of the cations amount to 2.79/3.40/0.41 Cs/unit cell (uc) for the Cs1/Cs2/Cs3 sites, respectively, and those of the water molecules to 4/4/4/4/8/4 H(2)O/uc for the Ow1/Ow2/Ow3/Ow4/Ow5/Ow6 sites, respectively. Close to water saturation, the Cs3 and Ow6 sites are near each other (approximately 1.44 A) and are not occupied simultaneously. At saturation, Cs cations and water molecules form three interconnected Cs(H(2)O)(n) clusters and one (H(2)O)(4) cluster in the MFI channel system: Cs2(H(2)O)(5) centered at x/y/z approximately -0.018/0.146/0.546 (midway between the intersection and the straight channels), Cs1(H(2)O)(4) centered at approximately 0.056/0.240/0.889 (the zigzag channel openings), Cs3(H(2)O)(2) centered at approximately 0.228/0.25/0.899 (in the zigzag channel), and the (H(2)O)(4) cluster (in the zigzag channel) bonded to Cs1 and Ow1. (H(2)O)(4) and Cs3(H(2)O)(2) exclude each other. The Cs2(H(2)O)(5) clusters are connected through weak Ow5...Ow5' hydrogen bonds (2.88 A) and form polymeric chains in the straight channel direction (010). During progressive hydration this Cs2 cation enlarges its hydration shell, stepwise, from Cs2(H(2)O)(2) to Cs2(H(2)O)(3), to Cs2(H(2)O)(4), and finally to a Cs2(H(2)O)(5) cluster. During the dehydration process, these extraframework species migrate, and it is shown that for varying total H(2)O/uc loadings the individual populations of the Cs(+) cations and H(2)O molecules strongly depend on experimental and measurement (in situ vs ex situ) conditions. The shapes of the channels change also; except for T > 150 degrees C, in all the Cs(6.6)H(0.3)MFI.xH(2)O phases, the straight channel D10R (double 10-ring) pore openings (1.16 < epsilon < 1.23) become strongly elliptical. The framework structure of all the investigated phases conforms to orthorhombic Pnma space group symmetry. Hydration and dehydration in Cs(6.6)MFI are fully reversible processes. From a knowledge of the Cs(+) locations, we are able to estimate, by computer simulations, the positions of H(2)O molecules in Cs(6.6)H(0.3)MFI.28H(2)O. The maximum theoretically possible water loading in an hypothetical and idealized cationless [Cs(6.6)H(0.3)]MFI structure amounts to 48 H(2)O/uc (nine independent water species), which is in fair agreement with existing high-pressure data (47 H(2)O/uc). This value is to be compared with the water saturation capacity obtained in a structural refinement of sealed-tube diffraction data of a proton-exchanged H(6.9)MFI.38H(2)O (seven independent water molecules). In the crystal structure of this H-ZSM-5 phase, the straight channel openings are almost circular (epsilon = 1.08). From this we conclude that the main factor responsible for the flexibility of the MFI framework is the presence of the Cs(H(2)O)(n)() clusters residing in, or close to, the straight channel double 10-rings.