Synthesis, characterization and studies on the third-order optical non-linearities of novel charge-transfer heteropoly complexes (C8H12N2)5H7PMo12O40 and (C8H12N2)3H3PMo12O40·5H2O

Summary Two novel charge-transfer (CT) heteropoly complexes, (C₈H₁₂N₂)₅H₇PMo₁₂O₄₀ (1) and (C₈H₁₂N₂)₃H₃-PMo₁₂O₄₀·5H₂O (2), prepared by reacting p-Me₂NC₆H₄NH₂ with the four-electron heteropoly blue H₇PMo₁₂O₄₀·12H₂O and heteropoly acid H₃PMo₁₂O₄₀· xH₂O, respectively, were characterized by elemental analysis, and u.v., i.r., XPS and e.s.r. spectroscopies. A sizable electron-transfer interaction occurs within the product molecules and the heteropoly anions retain their Keggin structure. Their third-order optical non-linearity coefficients were measured using the Z-scan technique at a concentration of 4.68 × 10⁻⁶ mol dm⁻³ for (1) and 2.79 × 10⁻⁶ mol dm⁻³ for (2), with I ₀ = 2.38 × 10¹³ w m⁻² and λ = 532nm. The |χ⁽³⁾| for (1) is 2.61 × 10⁻¹⁰ esu and |χ⁽³⁾| for (2) is 1.05 × 10⁻¹⁰ esu.     

Synthesis, Crystal Structure and Properties of Complex VO（C12H12N2O2） （C13H10NO2）

IntroductionAsthevanadate dependentenzyme ,ahaloperox idase,andvanadiumnitrogenasehavebeenfoundinsuccession ,somescientistsareinterestedinthecoor dinationchemistryandthebiochemistryofvanadi um[1] .Thereactivecenterofvanadiumbromoperoxi dasecontainstheoxovanadiumVO3+ coordinatedbyoxygenandnitrogenatoms[2 ] .However,thestudiesaboutoxovanadiumVO3+ coordinationcompoundscontainingbioactiveligandsarerarelyfound[3— 8] .Hydroximicacidthatcanbeconsideredtobethederivativeofthecarboxylicacid ,theamide…     

Synthesis and Characterization of H3PW12O40 and H3PMo12O40 Nanoparticles by a Simple Method

In this study H₃PW₁₂O₄₀·9H₂O and H₃PMo₁₂O₄₀·6H₂O (HPA) particles were changed into nano forms by heat-treatment in an autoclave as a simple, repaid, inexpensive and one step method. The particle size of these nanoparticles was around 25 nm. The as-synthesized nanostructures were characterized by dynamic light scattering, X-ray powder diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy and inductively coupled plasma analyzer. Thermal stability of nanoparticles was surveyed by thermal gravimeter analyse. Acidity of prepared nanoparticles was investigated by pyridine adsorption method. Results showed rising acidity by declining particle size of HPA.     

[Ni(C_5H_5N)_2(C_7·H_6O_2N)_2]H_2O三元配合物的合成及晶体结构

合成了标题化合物。该化合物的分子式[Ni(C5H5N)2(C7H6O2N)2]H2O(C24H24N4NiO3),分子量475.18,采用单色的MoKα (λ = 0.71073 )射线测定,共收集7408个数据,其中独立衍射点2567个(Rint = 0.0272),I > 2s(I)可观测点数1926个,结果表明该化合物属单斜晶系, 空间群C2/c其晶胞参数为: a = 14.466(2),b = 12.193(2),c = 14.072(2) ;β = 116.229(2)°,V = 2226.6(5) 3,Z = 4,Dc = 1.418 g/cm3 ,μ = 0.905 mm-1,F(000) = 992. 2个水杨醛亚胺各提供2个配位原子参与配位,2个吡啶各提供1个配位原子参与配位,该配合物是六配位的八面体构型,同时讨论了该体系中不同配位原子的配位能力的差异。     

Synthesis and structural characterization of a nonplanar neutral [36]metallacrown-12 nickel compound [Ni(C13H9N3O2)(CH3OH)]12

A nonplanar metallacrown [Ni-N-N]12 was achieved using a pentadente ligand, salicylaldehyde 2-pyridinecarboxylhydrazone (H2L) via a new modular self-assembly approach. The special bridging models of the ligand forced the macrocycle to form in a specific size with the wavelike conformation.     

H10[NiMoV12O40{Ni(H2O)3}4]的水热合成和晶体结构

在水热的条件下合成了1个标题的Mo-Ni-O异核簇合物，化学式为H34NiMo12O52(Mr=2311.10)，用单晶X射线衍射方法测定了它的结构，该晶体属四方晶系，I4l/amd空间群，晶胞参数为a=15.319(2),c=30.645(3)A,V=7191.2(16)A^3,Z=4,Dc=2.135g/cm^3,μ＝3．369mm^-1,F(000)=4376,1036个可观察衍射点（I＞2σ（I）），最终结构偏离因子R＝0．0560，wR=0.1632,S=1.002，该化合物簇阴离子笼中心是Ni^2 ，由12个MoO6八面体和4个NiO6八面体通过共角和共边构成。     

Synthesis and Crystal Structure of [VO2（C17H11N3O2） ] [VO （C4H13N3）（C6H5N3O） ]（C2H5OH）

The reaction of VO（acac）2 with 2-hydroxyl-1-naphthaldehyde isonicotinyl hydrazone and amines （ethylenediamine or diethylenetriamine） in CH3OH yields crystals of novel vanadium compounds characterized by IR, NMR spectroscopic methods and X-ray single-crystal structure determination. Two different vanadium units exist in the crystal cell of [VO2（C17H11N3O2）][VO- （C4H13N3）（C6H5N3O）]（C2H5OH） which crystallizes in the triclinic system, space group P1 with a = 8.0104（17）, b = 13.898（3）, c = 14.955（3）A, α = 89.103（4）, β = 79.551（4）, γ = 78.352（4）°, V = 1603.3（6）A^3, Mr = 723.54, Dc = 1.499 g/cm^3, Z = 2, λ（MoKα） = 0.71073 ]A,μ= 0.644 mm^-1, F（000） = 748, the final R = 0.0547 and wR = 0.0997 for 8920 observed reflections with I 〉 2σ（I）. According to structure analysis, two different molecules are arranged in the lattice and the two vanadium atoms adopt octahedral and square pyramidal coordination geometries, respectively. The interactions between DNA and vanadium complexes have been investigated by UV-Vis absorption spectro- photometry.     

H4 SiW12 O40 /C催化合成丁酮1,2-丙二醇缩酮

以丁酮和1,2-丙二醇为原料,活性炭负载硅钨酸（H4SiW12O40／C）为催化剂,催化合成了丁酮1,2-丙二醇缩酮。正交试验筛选出最佳反应条件为：丁酮200mmol,n（丁酮）：n（1,2-丙二醇）=1．0：1．4,ω（催化剂）=1．2％（以反应物质量计）,反应时间1h。在此最佳反应条件下,丁酮1,2-丙二醇缩酮的收率可达71．13％。     

(C5H7N2)3(AsMo12O40)·3C5H6N2·2H2O的水热合成、晶体结构及催化性能

采用水热法合成了一种新的3-氨基吡啶砷钼多金属氧酸盐配合物(C5H7N2)3(AsMo12O40)·3C5H6N2·2H2O。 通过单晶X射线衍射、红外光谱、紫外光谱和差热-热重对其进行了表征。 用催化消除丙酮的反应为模式反应,测试了配合物的催化性能。 研究结果表明,标题配合物是由Keggin结构[AsMo12O40]3-杂多阴离子、[C5H7N2]+阳离子、[C5H6N2]分子和结晶水分子组成。 配合物属于单斜晶系,P21/n空间群;晶胞参数a=1.33820(12) nm,b=2.2542(2) nm,c=1.9848(2) nm,β=100.27(3)°,V=5.8912(10) nm3,Z=4,Rgt(F)=0.0590,wRref(F2)=0.1882。 配合物对催化消除丙酮具有较好的的活性,催化实验结果表明,160 ℃下,0.20 g的催化剂可将初始浓度均为1.3 g/m3,流速为4.5 mL/min的丙酮完全消除。     

(C26H40N2O4)[Ln(NO3)5H2O]的合成及其铕缔合物的晶体结构

合成了4个新型的稀土化合物(C₂₆H₄₀N₂O₄)[Ln(NO₃)₅H₂O](Ln=Pr,Nd,Sm,Eu),采用元素分析和红外光谱表征,用四圆衍射仪测定了其中(C₂₆H₄₀N₂O₄)[Eu(NO₃)₅H₂O]的晶体结构,属三斜晶系,P1空间群,晶胞参数:α=0.9100(4)nm,b=1.3560(3)nm,c=1.6463(4)nm;α=68.62(2)°,β=74.84(3)°,γ=87.50(2)°;Z=2.中心铕离子由5个硝酸根的10个氧原子和1个水分子中的氧原子配位,配位数是11.1,7,10,16-四氧-4,13-二氮杂-N,N'-二苄基环十八烷(N,N'-二苄基穴醚(2,2))未参与配位.     

The crystal structure of phenoxatellurine dinitrate,C12H8O7N2Te

The crystal structure of phenoxatellurine dinitrate, C₁₂H₈O₇N₂Te, has been determined by x-ray diffractometer methods. The crystals are monoclinic, C2/c, a = 12.916(3), b = 14.050(5), c = 7.532(2) Å; β = 96.65(3)° at t = 22°. The molecule is nearly planar (175°), with the Te and O atoms of the central ring in special positions on the twofold symmetry axis. The bond distances for the central ring are: Te-C = 2.068(4) Å, C-O = 1.366(5), C-C = 1.388(6) with C-Te-C = 93.5(2)° and C-O-C = 128.2(5). The bond distances and angles in the phenyl rings do not differ significantly from the normally accepted values of 1.40 Å and 120°. The two nitrate groups are close to Te and are related by the twofold axis of symmetry. The independent distances and angles are: Te-O1 = 2.201(3), O1-N = 1.325(5), N-02 = 1.229(6), N-O3 = 1.204(6) Å, O2-N-O3 = 126.3(4), O1-N-02 = 117.1(4), O1-N-03 = 116.6(4)°. All hydrogen atoms were located at or near their calculated positions. The final R value for 1679 independent reflections was 0.031. The planarity of the molecule is discussed qualitatively in terms of simple molecular orbital theory.