四磺酸酞氰锌四钾盐的合成与表征

四磺酸酞氰锌四钾盐的合成与表征;四磺酸酞氰锌四钾盐;磺酸邻苯二甲酸单钾盐;磺酸邻苯二甲腈单钾盐;     

Synthesis, Characterization and Two-Photon Absorption Properties of a Novel Pyridinium Salt

A novel pyridinium salt, 2,4-bis[p-(N,N-dimethylamino)styryll-N-metlayl pyridinium iodide (BMSPI) was synthesized and characterized by TG, ^1H NMR spectroscopy and elemental analysis, and the reaction process was studied by using ES-MS. When BMSPI was pumped by a pulsed 1064 nm, 50 ps laser beam, it manifests highly efficient TPA (Two-Photon Absorption) and up-conversion superradiance. The up-conversion efficiency was 6.0% at the pump energy of 4-6 mJ and the lifetime of two-photon fluorescence was measured as 59 ps.     

Synthesis, Spectroscopic Properties and Structural Characterization of Sodium Potassium Citrato Oxotungstate(VI) Dimer

1　ＩＮＴＲＯＤＵＣＴＩＯＮＴｈｅｅｓｓｅｎｔｉａｌｒｏｌｅｏｆＭｏｉｎｖａｒｉｏｕｓｆｕｎｄａｍｅｎｔａｌｂｉｏｌｏｇｉｃａｌｃｏｎｖｅｒｓｉｏｎｓｃａｒｒｉｅｄｏｕｔｂｙｂｏｔｈｍｉｃｒｏｏｒｇａｎｉｓｍｓａｎｄｈｉｇｈｅｒｌｉｆｅｆｏｒｍｓｈａｓｂｅｅｎｋｎｏｗｎｆｏｒｄｅｃａｄｅｓ〔1〕.ＲｅｃｅｎｔｓｔｕｄｉｅｓｏｎｔｈｅｎｉｔｒｏｇｅｎａｓｅｅｎｚｙｍｅｈａｓｒｅｖｅａｌｅｄｉｔｓａｃｔｉｖｅｓｉｔｅｏｆＦｅＭｏ ｃｏ (ＦｅＭｏ ｃｏ ｆａｃｔｏｒ)ａｓａｃａｇｅ ｌｉｋｅＭｏＦｅ7Ｓ9ｈｏｍ…     

3,5-二羟基-2,4,6-三硝基苯酚氨基脲铵盐半水合物的合成、晶体结构和热分解特性

A new compound, semicarbazidium 3,5-dihydroxy-2,4,6-trinitrophenolate hemihydrate （SCDHTNP·0.5H2P）, was synthesized by the reaction of the aqueous solutions of semicarbazide with trinitrophloroglucinol. Its structure was determined by single-crystal X-ray diffraction analysis and characterized by elemental analysis, FTIR, DSC and TG-DTG techniques. The crystal is monoclinic with space group P21/n and the empirical formula C7H9N6O10.50. The unit cell parameters are： a= 1.3791（3） nm, b=0.9256（2） nm, c=2.0468（4） nm,β= 106.93（3）°, V=2.4995（9）nm^3, Z=8, Dc= 1.835 g/cm^3, Mr=345.20, F（000）= 1416, s=0.945,μ（Mo Ka）=0.174 mm^-1. The final R and wR are 0.0401 and 0.0896. Its structure consists of two semicarbazidium cations, two 3,5-dihydroxy-2,4,6-trinitrophenolate anions and one crystal water molecule, which are interconnected by electrostatic forces and hydrogen bonds into layer structure, making the title compound very stable. Under a linear heating rate, the thermal decomposition processes of SCDHTNP·0.5H2O have one endothermal dehydration stage and two intensive exothermic decomposition stages at 178-241℃ to evolve abundant gas products.     

Synthesis,characterization and thermal behaviour of four homoleptic titanium silanolates

Four titanium silanolates Ti(OSiR₂R′)₄ (1, R = Ph, R′ = ^tBu; 2, R = R′ = Ph; 3, R = R′ = ⁱPr; 4, R = Me, R′ = ^tBu) were synthesised starting from Ti(OⁱPr)₄ and the corresponding silanol, and their thermally induced decomposition was studied. Colourless single crystals of Ti(OSiPh Bu) CHCl C₇H₈ ( CHCl C₇H₈) were obtained from a mixture of chloroform and toluene (1:1) at ?20 °C. The compound crystallizes in the space group R3 c with Z = 18. The metal atom shows an almost ideal tetrahedral coordination, as is demonstrated by the O? Ti? O angles of 108.4(1)–111.1(1)°. Copyright © 2005 John Wiley & Sons, Ltd.     

三硝基均苯三酚及其碱金属盐晶体的周期性密度泛函理论研究

对三硝基均苯三酚(TNPG)及其碱金属盐晶体进行DFT-B3LYP周期性计算研究, 求得其能带和电子结构, 探讨了结构-性能关系. 研究结果表明, 晶胞结构参数的计算值与实验值吻合较好. TNPG的导电性介于半导体和绝缘体之间, 而其碱金属盐均为半导体. 金属离子的引入使TNPG阴离子和金属阳离子通过配位键形成三维无限网状结构, 这种网状结构与晶体的半导体性质相关联. TNPG及其碱金属盐的前线轨道主要是由C—NO₂的原子轨道组成, 配位水和金属离子对前线轨道的组成没有贡献. TNPG碱金属盐的带隙均比TNPG的小, 根据“最易跃迁原理”可推测碱金属盐均比TNPG敏感, 这与实验事实相符. 同时, 金属离子的引入增大了酚羟基上的氧原子的活性, 这也可能是导致碱金属盐比TNPG敏感的原因之一.     

混合价钼锗酸盐的合成、结构及性质研究

合成了单电子还原混合价杂多化合物 [C10H10N]4HGeMo12O40,并由元素分析、 IR、 UV进行了表征。单晶 X射线分析表明 ,属单斜晶系 ,空间群 P21/n,晶胞参数 a=1.4803(3),b=1.2582(3),c=1.7712(4)nm,β =98.31(3)° ,V=3.264(16)nm3。由 4296个可观察衍射点进行全矩阵最小二乘法修正后 ,可靠性因子 R=0.0646。变温 ESR研究表明随温度降低单电子离域程度减小。     

钾的N-酰化牛磺酸配合物的合成、表征及其晶体结构

The title complex(K(C₉H₁₃NO₅S₂)(H2O)) was synthesized by the reaction of p-tolysulfonyl chloride, taurine and potassium hydrate in water-methanol-ethanol solution. The crystal structure was determined by X-ray diffraction method and the chemical formula weight of the complex is 336.44. The crystal structure of the title complex belongs to orthorhombic space group Pbca and cell parameters: a=0.853 31(12) nm, b=0.820 42(12) nm, c=3.989 4(6) nm. V=2.792 8(7) nm³, Z=8, D_c=1.600 g·cm^-3, μ=0.699 mm^-1, F(000)=1 400. The compound is an one-dimension chain complex of infinite length which are connected with hydrogen bond and bridging coordination water. The difference and same of the complexes were discussed. CCDC: 244938.     

Preparation,Crystal Structure,Thermal Decomposition and Explosive Properties of K2（tza）2（H2O） （tza=Tetrazole-1-acetic Acid）

A new energetic compound based on the tetrazole-1-acetic acid (tza) and potassium(I) salt, K2(tza)2(H2O), was synthesized and characterized by elemental analysis and FT-IR spectrum. Its crystal structure was determined by single-crystal X-ray diffraction analysis. The results show that the crystal belongs to the orthorhombic system, space group Pna21 with a = 1.11972(17) nm, b = 0.46647(7) nm, c = 2.5158(4) nm, V = 1.3140(3) nm3, K2C6H8N8O5, Mr = 350.40 g·mol-1, Dc = 1.771 g·cm-3, μ(MoKα) = 0.759 mm-1, F(000) = 712, Z = 4, R = 0.023 and wR = 0.0527 for 2961 observed reflections (I > 2σ(I)). The K(I) cation is six-coordinated with four O atoms from three carboxylate groups, one O atom from one H2O molecule and one N atom from tetrazolyl ring, in which each tza is coordinated in a tridentate chelating bridging coordination mode. The thermal decomposition mechanism of the title complex was studied by DSC and TG-DTG techniques. Under nitrogen atmosphere at a heating rate of 10 K·min-1, the thermal decomposition of the complex contains one main exothermic process between 191.7 and 243.8 ℃ in the DSC curve. Its combustion heat was mensurated by oxygen bomb calorimetry. The non-isothermal kinetics parameters were calculated by the Kissinger's method and Ozawa-Doyle's method, respectively. The sensitivity properties of K2(tza)2(H2O) were also determined with standard methods, which was very sensitive to flame.     

Molten Salt Synthesis, Crystal Structure and Optical Properties of a Novel Quaternary Metal Selenide, K2AgIn3Se6

K2AgIn3Se6 was synthesized by a molten-salt (alkali-metal polyselenide flux) reaction at 500 ℃. The orange red granular crystal crystallizes in monoclinic space group C2/c with cell parameters, a=1.16411(7) nm, b=1.16348(8) nm, c=2.14179(12) nm, V=2.8740(9) nm^3, and Z=8. The crystal has a new two-dimensional structure containing ^2∞[AgIn3Se6]^2- anionic layers separated by K^- cations and the ^2∞[AgIn3Se6]^2- layer is constructed with corner-shared [AgSe4] and [InSe4] tetrahedra. The optical band gap of K2AgIn3Se6 was determined to be ca. 2.9 eV by UV/vis/NIR diffuse reflectance spectra.     

Speciation and Structural Properties of Hydrothermal Solutions of Sodium and Potassium Sulfate Studied by Molecular Dynamics Simulations

Aqueous solutions of salts at elevated pressures and temperatures play a key role in geochemical processes and in applications of supercritical water in waste and biomass treatment, for which salt management is crucial for performance. A major question in predicting salt behavior in such processes is how different salts affect the phase equilibria. Herein, molecular dynamics (MD) simulations are used to investigate molecular‐scale structures of solutions of sodium and/or potassium sulfate, which show contrasting macroscopic behavior. Solutions of Na?SO₄ exhibit a tendency towards forming large ionic clusters with increasing temperature, whereas solutions of K?SO₄ show significantly less clustering under equivalent conditions. In mixed systems (Na_xK_2?xSO₄), cluster formation is dramatically reduced with decreasing Na/(K+Na) ratio; this indicates a structure‐breaking role of K. MD results allow these phenomena to be related to the characteristics of electrostatic interactions between K⁺ and SO₄^2?, compared with the analogous Na⁺?SO₄^2? interactions. The results suggest a mechanism underlying the experimentally observed increasing solubility in ternary mixtures of solutions of Na?K?SO₄. Specifically, the propensity of sodium to associate with sulfate, versus that of potassium to break up the sodium–sulfate clusters, may affect the contrasting behavior of these salts. Thus, mutual salting‐in in ternary hydrothermal solutions of Na?K?SO₄ reflects the opposing, but complementary, natures of Na?SO₄ versus K?SO₄ interactions. The results also provide clues towards the reported liquid immiscibility in this ternary system.     

吡啶-2,6-二甲酸氢钾的合成、结构表征及热化学性质

合成了吡啶-2,6-二甲酸氢钾(KHDPC). 利用X射线单晶衍射仪确定了化合物的晶体结构. 用精密自动绝热热量计测量了其在78~360 K温度区间的低温热容. 利用最小二乘法对配合物的实验热容进行拟合, 得到热容随温度变化的多项式方程. 利用此方程计算出温度区间内的舒平热容值及相对于298.15 K时的热力学函数值. 利用Hess定律设计合理的热化学循环, 在等温环境下利用溶解-反应热量计分别测定所设计热化学反应的反应物和产物在所选溶剂中的溶解焓并计算出反应的反应焓. 最后, 计算出该化合物的标准摩尔生成焓为-(1052.69±1.52) kJ/mol.     

亚甲基蒽苯乙烯吡啶盐的合成、结构及双光子吸收性质

以氯化4-甲基-N-9-亚甲基蒽吡啶盐为原料,合成了一种新型的苯乙烯吡啶盐,通过红外、核磁共振氢谱、碳谱、电喷雾质谱、单晶X射线衍射等测试技术对化合物的结构进行了表征。单晶X射线衍射结果表明,该化合物属于单斜晶系,空间群为P21/c,晶胞参数a=1.255 7(1)nm,b=1.539(1)nm,c=2.220 2(8)nm,β=101.099(1)°,V=4.210 5(4)nm3,Z=4,Dc=1.159 g/cm3。用1 064 nm皮秒脉冲激光研究其三阶非线性光学特性,双光子吸收系数β=0.028 cm/GW,吸收截面为σ=8.68×10-48cm4.s.photon-1,表明目标化合物具有良好的三阶非线性光学性质。     

Preparation and Molecular Structure of (SCZ)(TNPG)·2H2O

The (SCZ)(TNPG)·2H2O prepared by mixing semicarbazide (SCZ) and trinitrophloroglucinol (TNPG) was characterized by elemental analysis and IR measurement, and its crystal structure was determined by X-ray single-crystal diffraction analysis.The crystal belongs to triclinic,0.93966(19), c = 1.1925(2) nm, α = 67.48(3), β = 77.56(3), γ = 78.93(3)°, V = 0.6908(2) nm3, Z = 2,Dc = 1.789 g/cm3, Mr = 373.23, F(000) = 384, S = 0.999 andt(MoKα) = 0.172 mm-1.The final R and wR are 0.0394 and 0.1057 for 1724 observed reflections with I ＞ 2σ(I).It is concluded that (SCZ)(TNPG) 2H2O is an ionic compound composed of a cation SCZ+, an anion TNPG- and two water molecules.The TNPG anion and SCZ+ cation are bonded together by electrostatic attraction and hydrogen bonds, and the compound structure is stable.The thermal decomposition of (SCZ)(TNPG) 2H2O was studied by using TG-DTG and DSC techniques with a heating rate of 10 ℃/min, showing the compound contains one endothermic process of dehydrating stage and two intensive exothermic decomposition stages.The enthalpy of exothermic decomposition reaction is 452.31 kJ/mol.     

柚皮素三乙胺盐一水合物的制备、晶体结构及溶解度

柚皮素是一种天然黄酮类化合物,几乎不溶于水。利用晶体工程学原理可以有效改善天然产物的溶解性。本文合成了柚皮素和三乙胺的有机盐一水合物[C_(15)H_(11)O_5]-·[C_6H_(16)N]+·H_2O,测定了其晶体结构。解析结果表明,有机盐水合物属于单斜晶系,P2_1/n空间群。柚皮素7取代位的羟基上的质子转移到了三乙胺的N原子上,并形成了N~+—H....O~-氢键。羟基阴离子与4'取代位上的羟基形成了O—H....O~-氢键,产生了一维的氢键链状结构。水分子通过两种氢键作用将一维的氢键链连接成二维的氢键网络。形成三乙胺盐一水合物后,柚皮素在水中的溶解度增加了20倍。     

Preparation and Molecular Structure of (SCZ)(TNPG)·2H_2O

1 INTRODUCTION 2,4,6-Trinitro-1,3,5-trihydroxybenzene(trinitro- phloroglucinol, TNPG) is a strong acidic organic com- pound with yellow needle crystal structure. There are three nitro-groups and three phenolic hydroxyl groups conjugated with the ring, so it is an important explosive. It can react with metallic compounds forming metallic salts of TNPG, which have strong combustion and detonating properties. The lead salt of TNPG has been extensively studied and recom- mended to use as…     

A Facile Method for the Synthesis of Binary Tungsten Iodides

The preparation of tungsten iodides in large quantities is a challenge because these compounds are not accessible using an easy synthesis method. A new, remarkably efficient route is based on a halide exchange reaction between WCl₆ and SiI₄. The reaction proceeds at moderate temperatures in a closed glass vessel. The new compounds W₃I₁₂ (W₃I₈?2 I₂) and W₃I₉ (W₃I₈? I₂) containing the novel [W₃I₈] cluster are formed at 120 and 150 °C, and remain stable in air. W₃I₁₂ is an excellent starting material for the synthesis of other metal‐rich tungsten iodides. At increasing temperature these trinuclear clusters undergo self‐reduction until an octahedral tungsten cluster is formed in W₆I₁₂. The synthesis, structure, and an analysis of the bonding of compounds containing this new trinuclear tungsten cluster are presented.     

无水烟酸钾的合成、表征及热化学

选择分析纯烟酸和无水醋酸钾为反应物, 利用室温固相合成方法, 合成了无水烟酸钾. 利用FTIR和X射线粉末衍射等方法表征了它的结构. 用精密自动绝热热量计测定了它在77～400 K温区的低温热容, 将该温区的摩尔热容实验值用最小二乘法拟合, 得到热容随温度变化的多项式方程. 用此方程进行数值积分, 得到此温区内每隔5 K的舒平热容值和相对于298.15 K时的各种热力学函数值. 在此基础上, 通过设计合理的热化学循环, 利用等温环境溶解-反应热量计分别测定固相反应的反应物和生成物在所选溶剂中的溶解焓, 从而得到该固相反应的反应焓为 (25.87±0.47) kJ•mol^－1. 最后, 依据Hess定律计算出烟酸钾的标准摩尔生成焓为 ＝－(560.57±1.09) kJ•mol^－1.     

Synthesis,Structure and Properties of Inverse-Keggin Potassium Tetraniobooctatungstosilicate

Ｓｙｎｔｈｅｓｉｓ，ＳｔｒｕｃｔｕｒｅａｎｄＰｒｏｐｅｒｔｉｅｓｏｆＩｎｖｅｒｓｅ－ＫｅｇｇｉｎＰｏｔａｓｓｉｕｍＴｅｔｒａｎｉｏｂｏｏｃｔａｔｕｎｇｓｔｏｓｉｌｉｃａｔｅＹＵＥＢｉｎ，ＴＡＮＧＬｉ－ｈａｏ，ＲＵＩＣｈｅｎｇ－ｇｕｏ，ＬＩＵＨｕｉ－ｚ...     

青霉素钾对CTAB胶束性质的影响

研究了青霉素钾对十六烷基三甲基溴化铵（CTAB）的cmc、CTAB胶束聚集数和扩散系数的影响.研究结果表明，青霉素钾(Pen K)的加入使得CTAB胶束的第一cmc、第二cmc上升；CTAB球形胶束的聚集数下降,扩散系数增加；CTAB棒状胶束的聚集数增加,扩散系数降低.