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1.
徐保莲  代坤  陈景文 《无机化学学报》2014,30(12):2733-2739
设计合成了4种含不同芳香取代基团的肼基二硫代甲酸甲酯配体(2-乙酰基吡啶肼基二硫代甲酸甲酯(L1-H)、2-甲酰基吡啶肼基二硫代甲酸甲酯(L2-H)、2-甲酰基噻吩肼基二硫代甲酸甲酯(L3-H)、2-甲酰基水杨醛肼基二硫代甲酸甲酯(L4-H))的镓配合物,对它们的抑菌活性进行了测试,并讨论了配体分子中不同芳香取代基对配合物抑菌活性的影响。在模拟生理条件下,L-H与Ga3+生成较稳定的单核配合物[Ga(L1)2]NO3(1)、[Ga(L2)2]NO3(2)、[Ga(L3)2]NO3(3)、[Ga(L4)2]NO3(4),各配合物对金黄色葡萄球菌和大肠杆菌表现出比Ga(NO3)3·9H2O强的抑制活性,抑制金黄色葡萄球菌的能力高于大肠杆菌,其中,1和2的活性比相应配体高,其余2个配合物与其配体之间无明显活性差异。L1-H和L2-H分子中吡啶基的较强吸电子效应可能是1和2具有较强抑菌活性的主要原因。4种配合物抑制黑曲霉生长的活性同样高于Ga(NO3)3·9H2O,其中3最强,并显著高于L3-H,其余配合物与相应配体间无活性差异。  相似文献   

2.
合成并通过单晶衍射、元素分析及红外光谱表征了配合物[Ni(L12]·2DMF (1),[Cu(L12]·THF·0.25MeOH·2.25H2O(2), [Ni(L22]·2MeOH(3)和[Cu(L22]·2EtOH (4)的结构(HL1:5-甲酰基-3,4-二甲基-吡咯-2-甲酸乙酯缩硫代氨基脲,HL2:5-甲酰基-2,4-二甲基-吡咯-3-甲酸乙酯缩4-异丙基氨基硫脲)。单晶衍射结果表明,除溶剂分子不同外,配合物1~4的结构相似。每个配合物的中心金属离子分别与来自2个阴离子L-配体的N2S2电子供体配位,采取扭曲的平面正方形配位构型。荧光光谱结果表明,配合物与DNA的相互作用强于其配体。  相似文献   

3.
合成并通过单晶衍射、元素分析及红外光谱表征了配合物[Ni(L12]·2DMF(1),[Cu(L12]·THF·0.25MeOH·2.25H2O(2),[Ni(L22]·2MeOH(3)和[Cu(L22]·2EtOH(4)的结构(HL1:5-甲酰基-3,4-二甲基-吡咯-2-甲酸乙酯缩硫代氨基脲,HL2:5-甲酰基-2,4-二甲基-吡咯-3-甲酸乙酯缩4-异丙基氨基硫脲)。单晶衍射结果表明,除溶剂分子不同外,配合物1~4的结构相似。每个配合物的中心金属离子分别与来自2个阴离子L-配体的N2S2电子供体配位,采取扭曲的平面正方形配位构型。荧光光谱结果表明,配合物与DNA的相互作用强于其配体。  相似文献   

4.
合成并通过单晶X射线衍射、元素分析及红外光谱表征了配合物[Cu(HL)Cl2]·H2O(1)和[ZnL2](2)的结构(HL为3-乙基-2-乙酰吡嗪缩肼基甲酸甲酯)。单晶衍射结果表明,在配合物1中,Cu(Ⅱ)离子拥有四方锥配位构型,与一个中性配体HL和2个氯离子配位。配合物2中,Zn(Ⅱ)离子与来自2个阴离子配体L-的N2O电子供体配位,配位构型为扭曲的八面体。此外还研究了配合物12的固体荧光性质。  相似文献   

5.
合成并通过单晶X射线衍射、元素分析及红外光谱表征了配合物[Cu(HL)Cl2]·H2O(1)和[ZnL2](2)的结构(HL为3-乙基-2-乙酰吡嗪缩肼基甲酸甲酯)。单晶衍射结果表明,在配合物1中,Cu(Ⅱ)离子拥有四方锥配位构型,与一个中性配体HL和2个氯离子配位。配合物2中,Zn(Ⅱ)离子与来自2个阴离子配体L-的N2O 电子供体配位,配位构型为扭曲的八面体。此外还研究了配合物12的固体荧光性质。  相似文献   

6.
以2-(N,N-二(2-吡啶甲基)氨甲基)-6-醛基-4-甲基苯酚(HL)为配体合成了一个新的双核钙配合物[Ca2L2(NO32](1)和一个单核镉配合物[Cd(HL)(NO32](2),在碱性条件下,2能转化为双核镉配合物[Cd2L2(NO32]·H2O(3)。分别对它们进行了红外、质谱、元素分析和单晶结构表征。配合物13属于单斜晶系,空间群分别为P21/cC2/c,配合物2属于三斜晶系,空间群为P1。单晶结构表明,配合物1含有一个酚氧桥连的双核钙单元[Ca2O2],每个钙均为八配位的扭曲十二面体构型[CaN3O5],配位原子分别来自一个配体L-的3个氮原子和一个酚氧原子、另一个配体L-的一个酚氧原子和一个醛氧原子以及一个硝酸根的2个氧原子。2是一个单核镉配合物,八配位镉的配位构型是扭曲的十二面体[CdN3O5],配位原子分别来自配体HL的3个氮原子和一个酚氧原子以及2个硝酸根的4个氧原子,醛基不参与配位。配合物3含有一个酚氧桥连的双核镉单元[Cd2O2],每个镉均为七配位的单帽三棱柱构型[CdN3O4],配位原子分别来自一个配体L-的3个氮原子和一个酚氧原子、另一个配体L-的一个酚氧原子和一个醛氧原子以及一个硝酸根的一个氧原子。  相似文献   

7.
利用配位驱动吡唑基配体在溶液中自发去质子自组装的方法,用金属转子[(bpy)2Pd2(NO32](NO32、[(dmbpy)2Pd2(NO32](NO3)2(bpy=2,2''-联吡啶,dmbpy=4,4''-二甲基-2,2''-联吡啶)和酰胺-吡唑双功能配体(HL1、HL2)合成了含有Pd(Ⅱ)…Pd(Ⅱ)相互作用的[Pd2L2]2+类型的吡唑基双钯(Ⅱ,Ⅱ)“夹子” C1~C4。利用1H和13C NMR、ESI-MS、红外光谱和X射线单晶衍射等测试手段对配合物C1~C4的结构进行了表征。同时,合成的夹子状双金属配合物对Suzuki-coupling反应均表现出较好的催化活性。  相似文献   

8.
分别以3-(2-吡啶基)-4-苯基-5-(2-呋喃基)-1,2,4-三氮唑(L1)和3-(2-吡啶基)-4-(对氟苯基)-5-(2-呋喃基)-1,2,4-三氮唑(L2)作为配体,合成了2个新的单核铜配合物:trans-[Cu (L12(NO32]0.5[Cu (L12(H2O)2]0.5(NO3)(1)和trans-[Cu (L22(NO32]0.5[Cu (L22(H2O)2]0.5(NO3)·2CH3OH (2)。对它们进行了红外、元素分析、热重分析、单晶结构和粉末X射线衍射表征。2个配合物都属于三斜晶系,P1空间群。单晶结构表明,配合物12中均有2个不同的铜离子,且都处于一个扭曲的八面体[CuN4O2]配位环境,但在轴向上一个铜离子与2个水分子配位,另一个铜离子则与2个硝酸根配位。配体的吡啶氮原子和三氮唑的一个氮原子参与配位,而呋喃的氧原子不配位。配合物晶体中存在C—H…N、C—H…O、O—H…O氢键和C—H…π相互作用,从而连接单核配合物形成二维层状结构。  相似文献   

9.
合成并通过单晶衍射、元素分析、红外光谱表征了配合物[Cd2(L)2(NO32](1)、[Fe (L)2]NO3·3CH3OH (2)和配体硝酸盐(H2L) NO3(HL=喹啉-2-甲醛缩4-氟苯基氨基硫脲)。单晶衍射结果表明,双核配合物1中,每个Cd(Ⅱ)离子与一个N2S供体L-、一个双齿配位的硝酸根和相邻缩氨基硫脲配体的μ2-桥联S原子配位,采取扭曲的八面体配位构型。配合物2中,Fe(Ⅲ)离子与来自2个三齿配体L-的4个N原子和2个S原子配位,同样采取扭曲的八面体配位构型。荧光光谱、紫外光谱以及粘度实验结果表明,配合物2与ct-DNA的结合模式为插入的结合方式,而配体HL和配合物1与ct-DNA以沟面结合的方式相互作用,且配合物2与ct-DNA的结合能力优于配体和配合物1。另外,细胞毒理实验结果表明3种化合物中配合物2具有最强的抑制HeLa肿瘤细胞增殖能力。  相似文献   

10.
合成并通过单晶衍射、元素分析、红外光谱表征了配合物[NiL2]·2CH3OH(1),[ZnL2]·CH3OH(2),[CdL2]·CH3CH2OH(3)和[Cu2L2Cl2](4)(HL为喹啉-8-甲醛缩4-甲基氨基硫脲)。单晶衍射结果表明,配合物1~3结构相似,中心金属离子与来自2个硫醇化脱质子配体L-的4个N原子和2个S原子配位,采取扭曲的八面体配位构型。而配合物4中Cu(Ⅱ)离子与1个中性配体HL和3个氯离子配位,其中2个氯离子为μ2桥联。荧光光谱结果表明,所有配合物,尤其是4与DNA的相互作用能力明显强于配体。  相似文献   

11.
Chalcone-derived 3-phenyl-1-pyridin-2-ylprop-2-en-1-one thiosemicarbazone (HPyCTPh) (1), 3-(4-chlorophenyl)-1-pyridin-2-ylprop-2-en-1-one thiosemicarbazone (HPyCT4ClPh) (2), 3-(4-bromophenyl)-1-pyridin-2-ylprop-2-en-1-one thiosemicarbazone (HPyCT4BrPh) (3), and 3-(4-nitrophenyl-1-pyridin-2-ylprop-2-en-1-one thiosemicarbazone (HPyCT4NO2Ph) (4) were obtained as well as their gallium(III) and zinc(II) complexes [Ga(PyCTPh)2]NO3 (Ga1), [Ga(PyCT4ClPh)2]NO3 (Ga2), [Ga(PyCT4BrPh)2]NO3 (Ga3), [Ga(PyCT4NO2Ph)2]NO3 (Ga4), [Zn(PyCTPh)2] (Zn1), [Zn(PyCT4ClPh)2] (Zn2), [Zn(PyCT4BrPh)2] (Zn3), and [Zn(PyCT4NO2Ph)2] (Zn4). The chalcones, thiosemicarbazones, and zinc(II) complexes were not active against Pseudomonas aeruginosa. The thiosemicarbazones proved to be more active than the parent chalcones against Staphylococcus aureus and Candida albicans. Coordination to zinc(II) resulted in activity improvement of most thiosemicarbazones against S. aureus. Coordination to gallium(III) significantly improved the antimicrobial activity of all thiosemicarbazones against the studied micro-organisms, suggesting this to be an effective strategy for antimicrobial activity enhancement.  相似文献   

12.
Four Ag(I) complexes, [Ag(L1)2](NO3) (1), [Ag(L2)(NO3)] (2), [Ag(L3)3](NO3) (3), and [Ag(L4)2](NO3) (4), with ligands derived from halo-containing cyanoanilines (L1 = 4-amino-3fluorobenzonitrile, L2 = 4-amino-3-chlorobenzonitrile, L3 = 4-amino-3-bromobenzonitrile, L4 = 4-amino-2-bromobenzonitrile) were synthesized and characterized by C, H, and N elemental analysis, IR and 1H NMR spectroscopy and single crystal X-ray diffraction. Complexes 14 crystallized in the triclinic space group C2/c, P2(1)/n, P-1 and C2/c, respectively. In 1 and 4, Ag+ is four-coordinate with L1 or L4 to form 1-D {[Ag(L1/L4)2]+} polymeric cations. In 2, Ag+ is three-coordinate by two L2 ligands and one NO3? ligand to form a 1-D {[Ag(L2)(NO3)]} zigzag chain. In 3, Ag+ is four-coordinate by L3 to form a dinuclear [Ag(L3)3]+ cation. The NO3? is a 4-connector bridging group in 1 and 3 and a 5-connector bridging group in 2 and 4. The intermolecular hydrogen bonds and Ag?O weak interactions play important roles in forming 3-D networks of 14. The antibacterial activities for 14 were evaluated against Bacillus subtilis, Staphylococcus aureus and Escherichia coli with MTT method. The antibacterial results indicated that 2 showed the best inhibitory activity against the test bacterial strains, and was as potent as chloramphenicol.  相似文献   

13.
Four Ru(II) complexes with tridentate ligands viz. (4-hydroxy-N′-(pyridin-2-yl-ethylene) benzohydrazide [Ru(L1)(PPh3)2(Cl)] (1), N′-(pyridin-2-yl-methylene) nicotinohydrazide [Ru(L2)(PPh3)2(Cl)] (2), N′-(1H-imidazol-2-yl-methylene)-4-hydroxybenzohydrazide [Ru(L3)(PPh3)2(Cl)] (3), and N′-(1H-imidazol-2-yl-methylene) nicotinohydrazide [Ru(L4)(PPh3)2(Cl)] (4) have been synthesized and characterized. The methoxy-derivative of L3H (abbreviated as L3H*) exists in E configuration with torsional angle of 179.4° around C7-N8-N9-C10 linkage. Single crystal structures of acetonitrile coordinated ruthenium complexes of 1 and 3 having compositins as [Ru(L1)(PPh3)2(CH3CN)]Cl (1a) and [Ru(L3)(PPh3)2(CH3CN)]Cl (3a) revealed coordination of tridentate ligands with significantly distorted octahedral geometry constructed by imine nitrogen, heterocyclic nitrogen, and enolate amide oxygen, forming a cis-planar ring with trans-placement of two PPh3 groups and a coordinated acetonitrile. Ligands (L1H-L4H) and their ruthenium complexes (1–4) are characterized by 1H, 13C, 31P NMR, and IR spectral analysis. Ru(II) complexes have reversible to quasi-reversible redox behavior having Ru(II)/Ru(III) oxidation potentials in the range of 0.40–0.71 V. The DNA binding constants determined by absorption spectral titrations with Herring Sperm DNA (HS-DNA) reveal that L4H and 1 interact more strongly than other ligands and Ru(II) complexes. Complexes 1–3 exhibit DNA cleaving activity possibly due to strong electrostatic interactions while 4 displays intercalation.  相似文献   

14.
The reactions between ceric ammonium nitrate, (NH4)2Ce(NO3)6, (CAN) and the bidentate phosphine oxides, 4,5-bis(diphenylphosphine oxide)-9,9-dimethylxanthene (L1), oxydi-2,1-phenylene bis(diphenylphosphine dioxide) (L2), 1,2-bis(diphenylphosphino)ethane dioxide (L3) and 1,4-bis(diphenylphosphino)butane dioxide, L4 have been investigated. The crystal structures of the molecular Ce(NO3)4L1 ( 1 ), and ionic [Ce(NO3)3L32][NO3]⋅CHCl3 ( 3 ), [Ce(NO3)3L32][NO3] ( 4 ) and the polymeric [Ce(NO3)3L41.5] [NO3] ( 5 ) and the cerium(III) complex [Ce(NO3)2L12][NO3] ( 2 ) are reported. The thermal stability of the complexes has been examined by thermogravimetry with the gaseous decomposition products analysed by infrared spectroscopy. Evolution of CO2 is found for both Ce(III) and Ce(IV) complexes with the later also forming NO2. The formation of the complexes in solution has been studied by 31P NMR spectroscopy and further complexes [Ce(NO3)3L12]+[NO3] and [Ce(NO3)2L13]2+2[NO3] identified in CD3CN solution. The complex ( 1 ) exists as a single molecular species in solution and is stable in dichloromethane whilst ( 3 ) decomposes on standing in both CD2Cl2 and CD3CN to Ce(III) containing species. Complexes of L2 have been identified by solution 31P NMR spectroscopy and these decompose in solution to give Ce(NO3)3L22. This study represents the first structural characterisations of Ce(IV) complexes with bidentate phosphine oxides.  相似文献   

15.
以3-乙基-2-乙酰吡嗪N(4)-(对甲苯)氨基硫脲(HL)为原料,合成了[Ga(L)2]NO3·4CH3OH(1)和[In(L)2]NO3·1.75CH3OH(2)两种新型配合物,并进行了X射线衍射分析表征。结果表明,配合物1和配合物2同构但具有不同数目的结晶甲醇分子。每个配合物的金属中心被2个拥有[N2S]供体的配体阴离子包围,采取扭曲的八面体配位几何。此外,荧光光谱表明配合物与DNA的相互作用强于配体。  相似文献   

16.
The composition of complexes formed upon the extraction of UVI and ThIV nitrates with O-n-nonyl(N,N-dibutylcarbamoylmethyl) methyl phosphinate (L) from solutions of nitric acid without additional solvent was determined by 31P NMR spectroscopy. The structures of the complexes formed were studied by IR spectroscopy. Uranium(VI) is extracted from 3 and 5 M solutions of HNO3 as the [UO2(L)2(NO3)2] complex, while thorium(IV) is extracted from 5 M HNO3 as the [Th(L)3(NO3)3]+·NO 3 complex. In both cases, ligand L has bidentate coordination. Ligand L contacts with 3 and 5 M nitric acid to form adducts L·HNO3 and L· (HNO3)2, respectively. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2460–2464, November, 2005.  相似文献   

17.
Sandwich coordination complexes, [LnIII(H3L)2]X3?solvents, of Tb(III), Eu(III), Dy(III), Ho(III) and Er(III) were prepared with two new zwitterionic ester-substituted tripodal amine ligands, tris((2-hydroxy-5-n-butyl benzoate)aminoethyl)-amine (H3L1) and tris((2-hydroxy-5-methyl benzoate)aminoethyl)-amine (H3L2). These ligands were synthesised by condensation of the appropriately substituted salicylaldehyde with tris(2-aminoethyl)amine (tren) followed by in situ reduction of the tris-imine to tris-amine. Subsequent 2:1 reaction with lanthanide(III) ions yields [LnIII(H3L)2]X3?solvents (L = L1, L2; X = Cl?, NO3?; solvents = MeOH or H2O). All complexes were characterised by microanalysis, infrared spectroscopy, high resolution mass spectrometry and solid-state photoluminescence measurements. The crystal structures of [TbIII(H3L1)2]Cl3·6MeOH, [Dy(H3L1)2]Cl3·6MeOH, [EuIII(H3L1)2]Cl3·6MeOH and [TbIII(H3L1)2](NO3)3 reveal high-crystallographic ?3 symmetry at the O6-coordinated octahedral lanthanide(III) ions and that the tripodal ligands are bound in zwitterionic form: the protons from the phenolic oxygens have migrated to the amino nitrogens. Photoluminescence measurements indicate various degrees of energy transfer of the ligand chromophore to the lanthanide ions, as both ligand and lanthanide emission features are observed. Despite the high-crystallographic symmetry and the likely small transverse magnetic anisotropy of the complexes, no evidence of slow relaxation of the magnetisation, characteristic of a single-molecule magnet, was observed for [TbIII(H3L1)2]Cl3·MeOH·3H2O, [DyIII(H3L1)2]Cl3·6H2O, [HoIII(H3L1)2](NO3)3·2H2O, [ErIII(H3L1)2]·H2O and [TbIII(H3L1)2](NO3)3 down to 2.0 K.  相似文献   

18.
Bis‐β‐ketoimine ligands of the form [(CH2)n{N(H)C(Me)?CHC(Me)?O}2] (LnH2, n=2, 3 and 4) were employed in the formation of a range of gallium complexes [Ga(Ln)X] (X=Cl, Me, H), which were characterised by NMR spectroscopy, mass spectrometry and single‐crystal X‐ray diffraction analysis. The β‐ketoimine ligands have also been used for the stabilisation of rare gallium hydride species [Ga(Ln)H] (n=2 ( 7 ); n=3 ( 8 )), which have been structurally characterised for the first time, confirming the formation of five‐coordinate, monomeric species. The stability of these hydrides has been probed through thermal analysis, revealing stability at temperatures in excess of 200 °C. The efficacy of all the gallium β‐ketoiminate complexes as molecular precursors for the deposition of gallium oxide thin films by chemical vapour deposition (CVD) has been investigated through thermogravimetric analysis and deposition studies, with the best results being found for a bimetallic gallium methyl complex [L3{GaMe2}2] ( 5 ) and the hydride [Ga(L3)H] ( 8 ). The resulting films ( F5 and F8 , respectively) were amorphous as‐deposited and thus were characterised primarily by XPS, EDXA and SEM techniques, which showed the formation of stoichiometric ( F5 ) and oxygen‐deficient ( F8 ) Ga2O3 thin films.  相似文献   

19.
采用Schiff碱配体2-乙酰吡啶缩邻氨基苯甲酰腙(L)分别与Cd(NO3)2·4H2O和Zn(CH3COO)2·2H2O进行配位反应,得到2个配合物[CdL(NO3)2·H2O](1)和[ZnL2](2).分别采用1H NMR、FTIR和元素分析等手段对化合物进行了表征,并测定了2个配合物的单晶结构.结构解析表明,配合物1属于单斜晶系,P21/n空间群,配合物2属于单斜晶系,P21/c空间群.对配体和配合物的体外抑菌活性进行了初步考察,结果表明,配体L和配合物1具有一定的抑菌活性.  相似文献   

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