Syntheses and Crystal Structures of Two Octamolybdate Compounds Modified by CuⅡ-Imidazole Cations

Two new polyoxomolybdate compounds,namely(CuIIL2)2[CuⅡ(HL)2]2[Mo8O26(HL)2].(H2O)4(1) and [CuⅡ(HL)2]2[β-Mo8O26](HL)2(2)(HL=imidazole),were designed and synthesized under hydrothermal conditions.X-ray diffraction analyses reveal that compound 1 consists of one Mo8O26(HL)24-cluster,two CuL2,two Cu(HL)22+,and four disassociated water molecules;and compound 2 is constructed by one β-Mo8O264-cluster,two Cu(HL)22+,and two uncoordinated imidazole molecules.     

Synthesis,Crystal Structure and Band Structure of Tb3Co4Sn（13）

A new intermetallic compound,Tb3Co4Sn13,has been synthesized by solid-state reaction of the corresponding pure elements in a welded tantalum tube at high temperature.Its crystal structure was established by single-crystal X-ray diffraction.Tb3Co4Sn13 crystallizes in cubic,space group Pm3n(No.223) with a = 9.5072(2) ,V = 859.33(3) 3,Z = 2,Mr = 2255.45,Dc = 8.717 g/cm3,μ = 34.369 mm-1,F(000) = 1906,and the final R = 0.0140 and wR = 0.0312 for 199 observed reflections with I > 2σ(I).The structure of Tb3Co4Sn13 belongs to the Yb3Rh4Sn13 type.It is isostructural with RE3Co4Sn13(RE = La,Ce),featuring a 3D [Co4Sn12] framework based on [CoSn6] trigonal prisms.The [CoSn6] trigonal prisms are interconnected via corner-sharing and Sn-Sn bonds to form a 3D [Co4Sn12] framework.The other Sn and Tb atoms are located in the spacers of the 3D framework.Band structure calculations indicate that Tb3Co4Sn13 is metallic.     

Synthesis,Crystal Structure and Theoretical Calculation of 1,1＇,5,5＇-Tetramethyl-2,2＇-diphenyl-4,4＇-[i-phenylene-bis（methylidy-nenitrilo）]di-1H-pyrazol-3（2H）-one

1,1',5,5'-Tetramethyl-2,2'-diphenyl-4,4'-[i-phenylenebis(methylidynenitrilo)]di-1H-pyrazol-3(2H)-one was synthesized and characterized by X-ray single-crystal diffraction analysis.The crystal crystallizes in monoclinic,space group P21/c with a = 6.1375(1),b = 24.6571(4),c = 17.7487(3) ,β = 94.781(1)°,V = 2676.62(8) 3,C30H28N6O2,Mr = 504.58,Z = 4,Dc = 1.252 g/cm3,F(000) = 1064,μ = 0.081 mm-1,R = 0.0463 and wR = 0.1153(I > 2σ(I)).Theoretical studies of the title compound were carried out by density functional theory(DFT) BLYP method,using ADF program package.It indicates that N(26) and N(41) are active sites of the title compound.     

A Novel Inorganic-organic Hybrid Borate with Unique One-dimensional Infinite Aluminium-oxygen Chains

A novel inorganic-organic hybrid borate,[Al2(fum)(H3BO3)(OH) 4]n·n(H3BO3) (1,H2fum = fumaric acid) ,has been synthesized and characterized by single-crystal X-ray diffraction,FTIR and elemental analysis. Crystal data for compound 1: orthorhombic,space group Pnma,a = 14.108(3) ,b = 6.9412(14) ,c = 14.995(3) ,V = 1468.3(5) 3,Z = 4,Mr = 359.72,Dc = 1.627 g/cm3,μ = 0.254 mm-1,F(000) = 736,the final R = 0.0492 and wR = 0.1650 with I > 2σ(I) . In compound 1,each AlⅢ ion is coordinated by six oxygen atoms to adopt a distorted octahedral geometry. Both fumarate anion and the coordinated boric acid act as bidentate bridging ligands to link two neighboring AlⅢ centers simultaneously. Each AlⅢ ion is bridged by two μ2-hydroxyl ligands to construct an infinite wave-like [Al2(fum)(H3BO3)(OH) 4]n chain. These one-dimensional chains form hydrogen bonds with free boric acid molecules giving rise to a three-dimensional supramolecular network.     

Hydrothermal Synthesis and Crystal Structure of a Novel Hexanuclear Copper（Ⅱ） Complex：[Cu_6（DPPZ）_4（btc）_4（H_2O）_8]·5H_2O

A new hexanuclear copper(Ⅱ) complex,[Cu 6 (DPPZ) 4 (btc) 4 (H 2 O) 8 ]·5H 2 O (1,DPPZ=dipyrido[3,2-a:2,3-c]phenazine,H 3 btc=1,3,5-benzenetricarboxylic acid),has been hydrothermally synthesized and structurally characterized by X-ray single-crystal diffraction,elemental analyses,IR,and thermogravimetric analysis.Its crystal structure is of triclinic system,space group P1 with a=12.489(4),b=14.234(5),c=14.484(5),α=82.848(4),β=79.399(4),γ=73.646(4)°,V=2421.2(13) 3,Z=1,Cu 6 C 108 H 78 N 16 O 37,M r=2573.17,D c=1.752 g/cm 3,μ=1.398 mm-1,F(000)=1308,GOOF=1.011,the final R=0.0495 and wR=0.1030 for 5420 observed reflections with I > 2σ(Ⅰ).In 1,four btc 3ligands act as bridges between six neighboring Cu atoms to form an unusual hexanuclear copper cluster.The clusters are further connected by two types of O-H···O and O-H···N hydrogen bonds,generating a three-dimensional supramolecular structure.In addition,intermolecular and intramolecular π-π stacking interactions further consolidate the three-dimensional supramolecular framework of 1.     

A Two-dimensional Metallic Oxide Constructed from Molybdenum Clusters and Ag（Ⅰ）-[3-（2-pyridyl）-pyrazole] Cationic Coordination Components

A new polyoxomolybdate compound [Ag 3 (HL) 4 ](PMo 12 O 40)] 1 (HL=3-(2-pyridyl)pyrazole) has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction,elemental analyses,TG and IR spectroscopy.The compound crystallizes in triclinic,space group P1 with a=10.375(3),b=12.076(3),c=13.196(4),α=84.170(4),β=71.961(3),γ=86.326(4)°,V=1563.1(7)3,C 32 H 28 Ag 3 Mo 12 N 12 O 40 P,M r=2726.52,D c=2.897 g/cm 3,μ(MoKα)=3.366 mm 1,F(000)=1284,Z=1,the final R=0.0587 and wR=0.1312 for 4139 observed reflections (I > 2σ(Ⅰ)).X-ray diffraction analyses reveal that the PMo 12 O 40 3clusters in compound 1 are linked by four Ag 3 (HL) 4 3+ units via the terminal oxygen atoms to form a two-dimensional architecture.The symmetrical unit of Ag 3 (HL) 4 3+ exhibits two distinct Ag(Ⅰ) environments:a two-coordinate {AgN 2 } site and a five-coordinate {AgN 3 O 2 } site which links to two molybdate clusters.     

Synthesis and Crystal Structure of 10-（3,4-Dichlorophenymethylidyne）-9,10-dihydrofluorene

A novel compound of 10-(3,4-dichlorophenymethylidyne)-9,10-dihydrofluorene (C20H12Cl2, Mr = 323.20) was synthesized via Knoevenagel reaction under microwave irradiation (500 w) within short reaction time (8 min), giving a high yield of product (87%). Its structure was determined by IR, 1H NMR, MS, elemental analysis and X-ray diffraction. The crystal of the new compound is of monoclinic system, space group P21/c with a = 12.8781(13), b = 16.5067(16), c = 7.4656(7), β = 103.567(2)o, V = 1542.7(3)3, Z = 4, Dc = 1.392 g/cm3, μ = 0.413 mm-1, F(000) = 664, R = 0.0569 and wR = 0.1342 for 3355 observed reflections with I > 2σ(I). The crystal structure involves a conjugated system which shows an olefin structure.     

表柔比星-镁体系与DNA相互作用初步研究

表柔比星是临床上用于治疗快速增殖肿瘤的药物。本文应用紫外、荧光、圆二色、黏度、凝胶电泳等方法研究了表柔比星-Mg2+体系与DNA的作用。结果发现:在pH=7.4时,表柔比星可与Mg2+形成稳定体系。加入DNA后表柔比星-Mg2+体系的紫外吸收明显降低;Scatchard图表明表柔比星-Mg2+体系对溴化乙锭(EB)与DNA的结合为竞争性抑制;同时此体系可使DNA-EB体系荧光偏振度增大;使DNA的热变性温度(Tm)上升;黏度增大;凝胶电泳表明表柔比星-Mg2+体系对pBR322DNA有非常好的切割活性;圆二色谱法表明随着表柔比星-Mg2+体系的加入,DNA碱基间作用能迅速减弱,二级结构发生了显著的变化。综上所述:表柔比星-Mg2+体系与DNA之间为嵌插作用;且表柔比星-Mg2+体系具有更好的切割活性。这些结果,可为合理改善药效和设计新药提供依据。     

α-单取代-1,2-环十二二酮单肟的合成及晶体结构

通过α-单取代环十二酮与亚硝酰氯反应合成了一系列α-单取代-1,2-环十二二酮单肟,它们的结构经1H NMR,13C NMR,ESI-MS和元素分析确证.X射线衍射和量子力学计算结果表明,α-单取代环十二酮与亚硝酰氯反应生成α-单取代-1,2-环十二二酮单肟时,生成产物具有[4233]-3-酮和[3333]-2-酮两种...     

高比表面积Cr_2O_3-α-AlF_3催化剂的制备和应用(英文)

采用炭硬模板法制备了高比表面积Cr_2O_3-α-AIF_3催化剂.该催化剂的合成过程主要包括三步:(1)将一定浓度的蔗糖溶液浸渍到Cr_2O_3-γ-Al_2O_3中,然后经过热处理,使得蔗糖分解为炭;(2)将含炭的Cr_2O_3-γ-Al_2O_3固体在400℃用HF气体进行完全氟化;(3)在高温下利用燃烧法除去炭硬模板.对所制备的催化剂进行了X射线衍射(XRD),氮气吸脱附曲线,氨气程序升温脱附(NH_3-TPD),透射电镜(TEM),扫描电镜(SEM)和X射线能量散射(EDX)技术表征.结果表明,氟化过程对Cr_2O_3-α-AIF_3催化剂比表面积有重要影响,在最佳实验条件下,能够得到比表面积为115 m~2·g~(-1)的催化剂.此催化剂对催化裂解二氟乙烷(HFC-152a)制备氟乙烯(VF)的催化活性明显高于直接氟化制备的Cr_2O_3-α-AIF_3催化剂,这是因为高比表面积的Cr_2O_3-α-AIF_3催化剂具有较大的酸量.