The synthesis of pyrazolo- and isoxazolo-[3,4-c]-pyrazole hemiazadicarbocyanine dyes

New substituted pyrazolo and/or isoxazolo-[3,4-c]-pyrazole hemiazadicarbocyanine dyes (IV_a-d, V_a-d, VI_a-d) were prepared via the synthesis of 4-arylidino-1-phenyl-3-benzoxazolium-2-yl-pyrazol-5-one (II_a-d) followed by their interaction with hydrazine hydrate, phenylhydrazine and hydroxylamine. Structures of the synthesised compounds were determined from analytical data and from spectra. The biological activity of IV, V and VI were tested against bacteria and fungi.     

三维开放框架结构的无机-有机杂化材料[Cu4(SiW12O40)（pyz）4]的合成与晶体结构

以α-Keggin型硅钨酸、碳酸铜和2-乙基-3-甲基吡嗪(pyz)为原料,通过水热方法合成了标题化合物。采用元素分析、红外光谱和单晶X-射线衍射法表征了该化合物的结构。晶体结构分析表明,该化合物属于正交晶系,Pna21空间群,晶胞参数a=2.238 38(4)nm,b=1.386 87(3)nm,c=2.151 07(3)nm,α=β=γ=90°,V=6.677 7(2)nm3,Z=4,F(000)=6 408,Dc=3.598 g/cm3。该化合物中一价铜离子首先被pyz配体连接成波浪型的一维链状结构,而(SiW12O40)4-阴离子作为三齿配体进一步连接这些链形成一个三维的框架结构。     

三维超分子化合物[Zn(C6H4O2N)2·(H2O)4]n的水热合成及晶体结构

用2-羧基吡啶和六水合氯化锌反应制备了一种新的三维氢键超分子配合物,经X-射线衍射分析确定了单晶结构。该晶体属单斜晶系,P2(1)/n空间群,晶胞参数为:a=9.836(2),b=5.2256(10),c=14.611(3),Mr=381.64,β=90.01(3)°,V=751.0(3)3,Z=2,Dc=1.688Mg.m-3,F(000)=392,μ=1.680mm-1,R=0.0258,wR=0.0612。共收集2159个衍射数据,其中1273个为独立衍射点(Rint=0.0332),可观测点数1139个(I>2σ(I))。结果表明,在组成该超分子体系的基本结构单元[Zn(C6H4O2N)2.(H2O)4]中,Zn(Ⅱ)离子形成六配位的畸变的八面体构型,配合物单元之间通过氢键OH…O相互连接,形成了无限延伸的具有网状结构的三维超分子体系。     

5-(4-叠氮呋咱基)-[1,2,3]三唑[4,5-c]并呋咱内盐的合成、晶体结构及性能

以3,4-二氨基呋咱为原料,经重氮化-叠氮化、氧化-环化等反应合成了一种新型无氢富氮含能材料5-(4-叠氮呋咱基)-[1,2,3]三唑[4,5-c]并呋咱内盐(AFTF);采用红外光谱、核磁共振、元素分析等方法表征了目标物的结构;获得了AFTF的单晶并进行了晶体结构解析;采用DSC方法研究了AFTF的热稳定性,初步探讨了氧化-环化反应机理;采用Gaussian 09程序CBS-QB3方法计算了AFTF的固相生成热,基于晶体密度和固相生成热,利用EXPLO5爆轰软件预估了AFTF的爆轰性能。结果表明,化合物AFTF晶体为正交晶系,空间群为P 2(1)2(1)2(1),晶胞参数为:a=8.1782(17),b=8.6446(18),c=11.521(2),V=814.5(3)3,Z=4,μ=0.151 mm^-1,F(000)=440;AFTF的熔点为101.02℃,热分解温度为186.39℃;AFTF晶体密度为1.795 g/cm 3(296 K),氮含量为63.6%,理论爆速为8.982 km/s,爆压为33.5 GPa,生成热为1178.9 kJ/mol,爆热为6450.8 kJ/kg,表明AFTF是一种爆轰性能优良的无氢富氮高能量密度化合物,有望应用于高能推进剂或气体发生剂领域;低熔点特性有望使其作为熔铸炸药载体使用。     

有机锡化合物[(o-ClC6H4CH2)3Sn]2O的合成、表征及晶体结构

合成了有机锡化合物[(o-ClC_6H_4CH_2)_3Sn]_2O,通过元素分析、红外光谱和核磁共振氢谱对其结构进行了表征。用X-射线单晶衍射测定了该化合物的晶体和分子结构。化合物晶体为三斜晶系,空间群P墿,a=10.319(3),b=11.073(4),c=11.110(4),α=118.278(4)°,β=104.898(4)°,γ=99.573(4)°,V=1016.6(6)3,Z=1,Dc=1.644Mg/m3,μ=1.655mm-1,F(000)=498,R=0.0305,wR=0.0734。锡原子呈畸变四面体构型。     

[Pb(DNI)_2(H_2O)_4]的制备和晶体结构

通过2,4-二硝基咪唑(2,4-DNI)的钠盐水溶液与硝酸铅的水溶液反应,制备出了2,4-二硝基咪唑铅配合物;采用自然挥发法培养出了适于X光结构测定的单晶,X射线衍射测定结果为,晶体属单斜晶系,空间群为Cc,晶体学参数为:a=6.517(3)×10-1nm,b=17.131(6)×10-1nm,c=14.082(7)×10-1nm,α=90.00(3)°,β=97.80(4)°,γ=90.00(4)°,V=1 557.5(12)×10-3nm3,Z=4,Dc=2.531 g/cm3,μ=11.001 mm-1,F(000)=1 120,最后偏离因子R为0.022 6。根据红外光谱、元素分析和X射线衍射分析结果,确定了2,4-二硝基咪唑铅配合物的化学组成为C6H10O12N8Pb,分子结构式为[Pb(DNI)2(H2O)4]。     

Molten salt synthesis,characterization, and formation mechanism of superfine (HfxZr1-x)B2 solid-solution powders

High-purity superfine (Hf_xZr_1-x)B₂ solid-solution powders with various chemical compositions (x = 0.2, 0.5, and 0.8) were successfully synthesized via molten salt synthesis technique at 1423 K using ZrO₂, HfO₂, and 20% excessive B as precursors within a KCl/NaCl molten salt for the first time. The results showed that the as-synthesized solid-solution powders exhibited the irregular polyhedral morphology with the average particle sizes of 170–185 nm and simultaneously possessed a single-crystalline hexagonal structure and good compositional uniformity from nanoscale to microscale. In addition, their formation mechanisms were well interpreted by analyzing the thermodynamics of the possible chemical reactions in the molten salt.     

Pyrolo[1,2:4,5]-1,4-dioxopyrazino[1,2:1,6]pyrido[3,4-b]indoles: a group of urokinase inhibitors, their synthesis, and stereochemistry-dependent activity

Antifibrinolytic agents are required during complex surgeries to decrease bleeding; their pro-thrombotic potency and efficacy in causing hemostasis has attracted much attention. To discover new inhibitors of urokinase with high selectivity for antifibrinolytic effects over pro-thrombotic effects, the 12-position of (5aS,12S,14aS)- and (5aS,12R,14aS)-5,14-dioxo-1,2,3,5,5a,6,11, 12,14,14a-decahydro-5H,14H-pyrolo[1,2:4,5]pyrazino[1,2:1,6]pyrido[3,4-b]indoles were modified with L-Ala, L-Asp, L-Phe, L-Trp, L-Lys, L-Ser, Gly, and L-Leu to provide 16 (5aS,12S,14aS) and (5aS,12R,14aS) derivatives. In a murine bleeding model, the (5aS,12S,14aS) derivatives containing L-Ala, L-Asp, L-Phe, and L-Trp induced blood coagulation for the treated mice; they also stimulated thrombus formation in a rat thrombosis model, but the other derivatives inhibited thrombosis. The most potent compound, the L-Asp derivative, showed a good therapeutic window: the minimum effective dose for coagulation was <1 nmol kg(-1), whereas at 10 nmol kg(-1), no pro-thrombotic effect was observed. This type of coagulation action was correlated with a mechanism of urokinase inhibition, and these results could lead to the discovery of novel urokinase inhibitors.     

配合物[Co（C6H4O2N）2（H2O）4]的合成与晶体结构

采用水热法,用氯化钻与异烟酸反应得到了分子式为[Co（C6H4O2N）2（H2O）4]的配合物,通过X-射线单晶衍射研究了其结构。该配合物的晶体属三斜晶系,空间群P-1,晶胞参数a=0．63736（19）nm,b=0．6921（2）nm,c=0．9282（3）nm,α=96．051（3）°,β=104．703（3）°,γ=0．113084（3）°,V=0．35454（18）nm^3,Z=1,Dc=1．757g／cm^2,Mr=375．20,F（000）=193,μ（MoKa）=1．257mm^-1,R1=0．0834,wR2=0．2302[I〉2σ（I）],晶体由具有六配位的畸变八面体结构的两性离子通过氢键和面．面π-π堆积构成。     

二维层状超分子化合物[Mn（C8H5NO6）（H2O）2]n的合成及晶体结构研究

分子间的弱相互作用在配位化合物中往往表现为配合物分子内和(或)分子间的配体间相互作用。因此,研究配合物中的配体间弱相互作用就成为由配位化学向超分子化学过渡的桥梁。本文以锰离子为中心离子,以2,4,6-吡啶三羧酸为配体进行晶体合成实验。通过检测手段了解了合成的配合物配体间的弱相互作用。     

水热合成阻燃剂Zn[B_3O_4(OH)_3]及其结构的探讨

在水热的条件下合成了硼酸锌Zn[B3O4(OH)3],用组装合成的思想来描述该化合物的结构。该化合物系三硼氧聚阴离子B3O5(OH)3通过共享环外氧原子形成一维无限链,三硼氧聚阴离子链通过与ZnO4或氢键作用连接起来的网状结构。使用红外光谱、热重分析及X射线单晶衍射分析手段对该化合物结构进行了表征。该化合物属单斜晶系,P21/n空间群,晶胞参数a=6.8482(4),b=9.7967(6),c=7.7014(4),β=107.0290(10),V=494.03(5)3,Z=4。     

新型杂环Schiff碱的合成、晶体结构及荧光性质研究

以3-甲基-2-噻吩甲醛和4-氨基安替比林为原料合成了一种新的schiff碱--1,5-二甲基-4-[(3-甲基噻吩-2-亚甲基)氨基]-2-苯基-1,2-二氢吡唑-3-酮,采用IR、元素分析法、NMR及X-射线单晶衍射法对其结构进行了表征.该化合物属于正交晶系,P212121空间群,晶胞参数a=0.697 81(6)...     

8-硫-1,6-二氮双环[4.3.0]壬烷-7,9-二酮的合成及单晶结构

以二硫化碳、甲醇、氢氧化钾为起始原料,经3步反应生成5-甲氧基-1,3,4-噻二唑-2(3H)-酮,再与1,4-二溴丁烷进行取代,然后脱甲基,最后发生亲核取代反应得到8-硫-1,6-二氮双环[4.3.0]壬烷-7,9-二酮。通过熔点、1HNMR、13CNMR、元素分析及X射线衍射分析等方法对产物的结构进行了表征,目标化合物属于三斜晶系,P1空间群,晶胞参数a=0.784 00(16)nm,b=1.046 4(2)nm,c=1.051 4(2)nm,α=63.84(3)°,β=79.62(3)°,γ=89.42(3)°,V=0.759 2(3)nm3,Z=4,wR(F2)=0.125,μ=0.37 mm-1。     

New 2-pyridinealdehyde N 4-hydroxyethyl thiosemicarbazone and their Cd(II) and Cu(II) complexes: synthesis,spectral, in vitro antibacterial activity and molecular and supramolecular structure study

N ⁴-hydroxyethyl-pyridinealdehyde thiosemicarbazone (HL, 1) as a tridentate Schiff base has been synthesized by 1:1 reaction of S-methyl-3-((pyridyl)methyl) dithiocarbazate and 2-aminoethanol. Complexes [Cd(HL)₂](NO₃)₂ (2), [Cd(HL)I₂] (3), [Cd(HL)Cl₂] (4), [Cu(HL)₂](NO₃)₂ (5) and [Cu(HL)Cl₂] (6) have been obtained and characterized by elemental analyses, molar conductivities, and spectroscopic studies. The ligand molecule binds the metal ion using pyridyl nitrogen, azomethine nitrogen and the sulfur atoms. The crystal structure analysis of 3 has been determined and showed to be a distorted square pyramidal geometry complex. The inter- and intramolecular interactions give rise to a supramolecular network. Compounds 2, 3, 5 and 6 were assayed for their bioactivities against selected pathogens. Copper(II) complexes 5 and 6 showed antimicrobial activities against Gram-positive (Bacillus anthracis) and Gram-negative (Pseudomonas aeruginosa and Yersinia pseudotuberculosis) bacteria, complexes 2–4 showed antimicrobial activities against Bacillus atrophaeus, while the ligand itself showed antimicrobial activities against Escherichia coli and Y. pseudotuberculosis.     

一维链状均苯三酸锌配合物[Zn_3(BTC)_3(H_2O)_(12)]_n的水热合成及晶体结构研究

以Zn(CH3COO)2和均苯三酸(1,3,5-苯三酸)为原料,采用水热法合成了一维链状均苯三酸锌配合物[Zn3-(BTC)3(H2O)12]n,利用元素分析、X射线单晶衍射对其结构进行了表征。该配合物属于单斜晶系,C2空间群,a=17.424(5)nm,b=12.919(5)nm,c=6.577(5)nm,β=111.968(5)°,V=1.373 0(12)nm3,Z=2,Dc=1.999 g/cm3,μ=2.707 mm-1,F(000)=840,R1=0.031 5,wR2=0.078 9。     

Synthesis, optical characterization and crystal and molecular X-ray structure of a phenylazojulolidine derivative

The synthesis, spectroscopic characterization, and X-ray crystal structure of [4-(2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinolin-9-ylazo)-phenyl]-methanol azodye are reported. A 37-47 nm bathochromic shift has been observed by comparison with analogous azodyes where diethylamino or dimethylamino groups act as donor moiety in agreement with the larger electronic donating properties of julolidine. The azobenzene skeleton adopts a planar trans-configuration and intra- and inter-molecular hydrogen bonds have been detected. A correlation between the spectroscopic and the molecular features has been attempted.     

配位聚合物[Zn(phen)(H2O)2SO4]n的合成与晶体结构

通过扩散法得到了一个新的配位聚合物[Zn(phen)(H2O)2SO4]n[phen=邻菲啰啉]。通过X-ray单晶衍射对配合物的结构进行了表征。配合物属单斜晶系,Cc空间群,晶胞参数:a=15.1399(10),b=14.1420(10),c=6.6994(5),α=90°,β=103.458(1)°,γ=90°,V=1395.01(17)3,Z=2,μ=0.752 mm-1,R1=0.0214,wR2=0.0602。     

Novel aminated benzimidazo[1,2-a]quinolines as potential fluorescent probes for DNA detection: Microwave-assisted synthesis, spectroscopic characterization and crystal structure determination

A synthesis of novel benzimidazo[1,2-a]quinolines, substituted with piperidine, pyrrolidine and piperazine nuclei has been accomplished using an uncatalyzed amination protocol under microwave heating. All compounds were characterized by means of ¹H, ¹³C NMR, IR, UV/Vis and fluorescence spectroscopy. Crystal and molecular structures of 2-chloro- and 2-piperidinyl-benzimidazo[1,2-a]quinoline-6-carbonitrile were determined by X-ray diffractometry. These molecules are essentially planar. Their molecular assembly is characterized by the existence of weak intermolecular hydrogen bonds of C-H⋅⋅⋅N type and π-π aromatic interactions. The π-π aromatic stacking observed in the solid state structures of the 2-chloro- and 2-piperidinyl- derivatives are not analogous. The spectroscopic properties of these amino substituted benzimidazo[1,2-a]quinolines as their hydrochloride salts in the presence of ct-DNA were studied by means of fluorescence spectroscopy. Comparison of binding properties of amino substituted benzimidazo[1,2-a]quinoline hydrochloride salts to ct-DNA revealed significantly enhanced fluorescence emission intensity and thus offer the potential applications as a DNA-specific fluorescent probes.     

含取代吡唑基的1,2,4-三唑并[3,4-b]-1,3,4-噻二唑类化合物的合成与波谱表征

通过3-烷基／芳基-4-氨基-5-巯基-1,2,4-三唑与1-苯基-3-甲基-5-氯吡唑甲醛进行分子内的Mannich反应,合成了12个标题化合物,并经元素分析、红外光谱、核磁共振氢谱确证结构,讨论了,其波谱性质。