Ni（Ⅱ）,Cu（Ⅱ）,Zn（Ⅱ）的硝酸盐与氟哌酸的固态配合物的 …

由氟哌酸与Ｎｉ（Ⅱ）、Ｃｕ（Ⅱ）、Ｚｎ（Ⅱ）的硝酸盐合成了三个未见报道的固态配合物,并用元素分析、摩尔电导、红外光谱、热重分析表征了它们的组成和性质。     

铁(Ⅱ)异腈配合物与三甲基胺氮氧化物氧原子转移反应动力学及其机理研究

在CH2 Cl2 介质中研究了铁 (Ⅱ )异腈配合物 [FeL5(CN) ]Br(1 ,L = CNCH2 Ph)和trans [FeL4(CN) 2 ] (2 ,L = CNCH2 Ph)等与氧原子转移试剂 (CH3) 3NO的反应动力学行为 ,研究结果表明 :配合物 1与 (CH3) 3NO反应遵从二级速率定律 ,反应速率 =k2 [铁异腈配合物 ]× [(CH3) 3NO]。反应的活化熵ΔS≠ 和活化焓ΔH≠ 分别为- 2 5 34± 1 67cal·(mol·K) - 1 和 1 2 71± 0 49kcal·mol- 1 ,而配合物 2不与氧原子转移试剂反应。认为反应以缔合机理进行。     

壳聚糖与不同金属锌盐配位的红外光谱研究

用壳聚糖和硫酸锌合成了一系列不同配比的配合物。通过对这些配合物红外光谱的分析和比较,考察了主要吸收峰随不同配比的变化规律,照发了它们的主要红外吸收峰,研究还表明,不同锌盐与壳聚糖形成的配合物有不同的配位环境。     

金属-糖胺配合物的合成,光谱表征及催化酯类水解的动力学研究

合成了4种新的糖胺 金属配合物,分别为[Ni(HL) (H2 O) 2 ]2 Cl2 ·CH3OH·2H2 O ,[Cu(HL) ]2 Cl2 ·CH3CH2 OH·3H2 O ,[Zn(HL) ]2 Cl2 ·H2 O ,[Co(HL) (H2 O) (OH) ]2 Cl2 ·CH3OH·2H2 O (HLN ,N′ 二βD 葡萄糖基乙二胺) ,并用元素分析、红外、紫外、核磁共振氢谱对其结构进行了表征。结果表明,Ni(Ⅱ) ,Co(Ⅲ)配合物为八面体构型,而Cu(Ⅱ) ,Zn(Ⅱ)配合物为四面体构型。最后研究了其对对硝基苯吡啶甲酸酯(PNPP)催化水解的催化速率常数。     

叶绿素a锰（Ⅲ）和叶绿素a锰（Ⅱ）的合成和光谱

叶绿素ａ锰（Ⅲ）（Ｍｎ（Ⅲ）－Ｃｈｌ－ａ）由脱镁叶绿素（Ｐｈｅｏ－ａ）和醋酸锰（Ⅱ）合成而得，用反相高效液相色谱法分离纯化，叶绿素ａ锰（Ⅱ）（Ｍｎ（Ⅱ）－Ｃｈｌ－ａ）用Ｎａ２Ｓ２Ｏ４还原时绿素ａ锰（Ⅲ）获得，研究了它们的元素分析（ＥＡ），紫外可见吸附光谱（ＵＶ－Ｖｉｓ）和傅里叶红外吸收光谱（ＦＴ－ＩＲ）证明了此二种配合物的合成，并给出了（Ｍｎ（Ⅲ）－Ｃｈｌ－ａ）与（Ｍｎ（Ⅱ）－Ｃｈｌ－ａ）的组成分     

Synthesis and Characterization of New Cationic Fe(III),Co(II) and Ni(II) Complexes Containing Isatin/Triphenylphosphine Mixed Ligands

New cationic Fe(III),Co(II) and Ni(II) mixed ligand complexes containing both triphenylphosphine and isatin ligands were prepared and characterized using conventional physical and chemical methods of analysis

(I.R., UV-Vis., and ¹H NMR). Microanalytical data of the investigated complexes are consistent with the formulations. [Fe(Isa)₂ {P(Ph)₃}₂]³⁺, [Co(Isa)₂ {P(Ph)₃}₂]²⁺ and [Ni(Isa)₂ {P(Ph)₃}₂]²⁺, (Where Isa = Isatin and P(Ph)₃ = Triphenylphosphine).

The prepared complexes are soluble in polar solvents and could be of potential use in bio-inorganic applications.     

二亚胺混配镍(Ⅱ),铜(Ⅱ),锌(Ⅱ)配合物的电子光谱与感光氧化特性

报道了新近合成的马来腈二硫纶·5-硝基-邻菲咯啉混配镍(Ⅱ)、铜(Ⅱ)、锌(Ⅱ)配合物MLL’(L=mnt~(2-),1,2-二氰基乙烯-1,2-二硫醇离子,L’-5-NO_2-Phen,5-硝基-1,10-邻菲咯啉)在二甲基亚砜(DMSO),二甲基甲酰胺(DMF),乙二醇二甲醚(DME),乙醇(C_2H_5OH),四氢呋喃(THF),乙腈(CH_3CN)和二氯甲烷(CH_2Cl_2)中的电子吸收光谱,研究了电子光谱吸收带在相关分子轨道能级图中的对应跃迁关系,讨论了标题配合物有价值的配体间荷移跃迁(LL’CT)吸收带的本质特征及其影响因素,探讨了它们在DMSO中的感光氧化特性。     

原子分子在Ni(100)表面吸附的第一性原理研究

本文采用密度泛函理论,结合周期性平板模型,通过对原子H、N、O、S和C,分子CO、N2、NH3、NO,以及自由基CH3、CH、CH2、OH在Ni(100)表面吸附的研究,比较了它们的吸附能,稳定吸附位点,吸附结构及扩散能垒等信息. 这些吸附质与表面结合能力从小到大依次是N2相似文献   

Infrared Spectra of Some Metal (II) Complexes of 2-Aminomethylpyridine

Abstract

Band assignments in the IR spectra (700–150 cm^?1) of [M(amp)₃] (ClO₄)₂ (amp = 2-aminomethylpyridine; M = Mn(II), Fe(II), Co(II), Ni(II), Zn(II), [Zn(amp)₂Cl₂] and [Pt(amp)Cl₂] derived from amp-ND₂, their unlabelled analogues, [Zn(amp)₂X₂] (X = Br, I) and [Pt(amp)Br₂] are discussed.     

原子分子在Ni(100)表面吸附的第一性原理研究

本文采用密度泛函理论,结合周期性平板模型,通过对原子H、N、O、S和C,分子CO、N2、NH3、NO,以及自由基CH3、CH、CH2、OH在Ni(100)表面吸附的研究,比较了它们的吸附能,稳定吸附位点,吸附结构及扩散能垒等信息.这些吸附质与表面结合能力从小到大依次是N2NH3COCH3NOHOHCH2CNSONCHC.在所有的原子中,O原子倾向于吸附在桥位,而其余的原子则倾向于吸附在空位.除N2之外的分子吸附物(CO、NO、NH3),最佳吸附位点均为四重空位,而N2的最稳定吸附位置为顶位.对于自由基吸附物(CH、CH2、CN、OH)而言,它们倾向于吸附在四重空位,而CH3则稳定吸附在桥位.     

Co（Ⅱ）,Ni（Ⅱ）非有机溶剂液—液萃取行为的研究

In PEG-Eriochrome cyanine R-(NH4)2SO4 system the liquid-liquid extraction behaviour of Co(II) and Ni(II) without organic solvents was investigated. We found that Ni(II) was almost extracted by PEG phase while Co(II) was not extracted in the water solutions of NaAc-HAc (pH=5) and (NH4)2SO4. Thus Co(II) was quantitatively separated from mixed solutions of Ni(II) and Co(II) ions.     

Mononuclear Co(III) and Ni(II) Complexes with Polypyridyl Ligands, [Co(phen)2(taptp)]3+ and [Ni(phen)2(taptp)]2+: Synthesis, Photocleavage and DNA-binding

Two novel, mixed ligand complexes of cobalt(III) and nickel(II), [Co(phen)₂(taptp)]³⁺ (1) and [Ni(phen)₂(taptp)]²⁺ (2) (phen = 1,10-phenanthroline and taptp = 4,5,9,18-tetraazaphenanthreno [9,10-b]triphenylene), were synthesized and characterized by elemental analyses, UV-visible and NMR spectroscopies. The binding interactions of the two complexes with DNA have been investigated using absorption and emission spectroscopy methods and electrophoresis measurement mode. The intrinsic binding constants for these complexes to DNA are in the order of 10⁵. In Tris buffer, the Co(III) complex shows a moderate luminescence which was enhanced after binding to DNA. However for complex Ni(II), no emission was observed in Tris buffer. The [Co(phen)₂(taptp)]³⁺ and [Ni(phen)₂(taptp)]²⁺ can cause the photocleavage of DNA supercoiled pBR322 upon irradiation by 360 nm light. Based on the data, an intercalative mode of DNA binding is suggested for the two complexes.     

2,6-双[N-(1′,1′-二甲基-2′-羟基)甲酰胺]吡啶及镍(Ⅱ)配合物的合成与光谱学研究

合成并表征了有机配体2,6-双[N-(1′,1′-二甲基-2′-羟基)甲酰胺]吡啶(L)及其镍(Ⅱ)配合物,采用元素分析确定目标配合物组成为C15H21N3O4Ni.H2O,通过对比分析的方法讨论了配位前后游离配体L和镍(Ⅱ)配合物的核磁共振氢谱、核磁共振碳谱、红外吸收光谱和紫外-可见吸收光谱的谱学性质,进而推断出镍(Ⅱ)配合物的结构。结果表明,配体2,6-双[N-(1′,1′-二甲基-2′-羟基)甲酰胺]吡啶以2个酰胺负离子N和1个吡啶环N原子为配位原子,与中心金属离子Ni(Ⅱ)通过三齿形式配位;配合物中Ni(Ⅱ)采取dsp2杂化轨道方式与配位原子构成配位键,中心金属Ni(Ⅱ)的配位数为4,1个Ni(Ⅱ)与1个三齿配体L和1个水分子配位,形成平面正方形构型的低自旋镍(Ⅱ)配合物。     

配合物Zn3(NCS)6(L1)6(NO3)2及Ni3(NCS)6(L2)6(NO3)2的合成、光谱表征及荧光性质

以去离子水为溶剂,合成了以Zn2+及N12+为中心,以L1,L2[L1=4-氨基-3,5-二甲基-1,2,4-三唑,L2=4-氨基-1,2,4-三唑]及硫氰酸根为配体的两种配合物,对其进行了元素分析、金属离子络合滴定、摩尔电导测定,确定了配合物组成分别为Zn3(NCS)6(L1)6(NO3)2及Ni3(NCS)6(L2)6(NO3)2,同时对两种配合物做了红外光谱、紫外光谱及荧光光谱的测试表征.荧光光谱的测试表明两种配合物均在415 nm有一强的荧光发射峰,且镍配合物的荧光要明显强于锌配合物,两种配合物有望成为蓝光发光材料.     

Chemical modification of silica gel with synthesized new Schiff base derivatives and sorption studies of cobalt (II) and nickel (II)

In this study, three Schiff base ligands and their complexes were synthesized and characterized by infrared spectroscopy (IR), thermogravimetric analyses (TGA), nuclear magnetic resonance (NMR), elemental analysis and magnetic susceptibility apparatuses. Silica gel was respectively modified with Schiff base derivatives, (E)-2-[(2-chloroethylimino)methyl]phenol, (E)-4-[(2-chloroethylimino)methyl]phenol and N,N′-[1,4-phenilendi(E)methylidene]bis(2-chloroethanamine), after silanization of silica gel by (3-aminopropyl)trimethoxysilane (APTS) by using a suitable method. Characterization of the surface modification was also performed with IR, TGA and elemental analysis. The immobilized surfaces were used for Co(II) and Ni(II) sorption from aqueous solutions and values of sorption were detected by atomic absorption spectrometer (AAS).     

三种不同的钒氧簇合物的合成和光谱研究

利用水热法合成了三种钒氧簇合物：[{Ni(phen)₂}₂V₄O₁₂]H₂O (Ⅰ),[N(CH₂CH₂)₃NH]Na(H₂O)₆{K₄(H₂O)₄ [V₁₀O₂₈]}(H₂O)₄ (Ⅱ)和[(CH₃)₄N]₆[V₁₅O₃₆Cl] (Ⅲ)。通过用FTIR, UV-Vis DRS和荧光光谱研究了它们的结构和性能的关系。FTIR研究表明,化合物的相关基团的特征振动吸收峰和其结构相关。化合物Ⅰ的固体紫外漫反射光谱在200, 230, 260和350 nm出现四个宽峰,分别对应O_t→V, O_μ→Ni,O_μ→V荷移和phen的π-π*跃迁。文章还对这三个钒氧簇合物的荧光光谱进行了研究。最后,应用Gaussian98的量子化学计算,说明化合物Ⅰ的结构特点。     

Design and Synthesis of a Ruthenium(II) Complex-Based Luminescent Probe for Highly Selective and Sensitive Luminescence Detection of Nitric Oxide

Nitric oxide (NO) is one of the most important intercellular signaling molecules, and plays important roles in various biological systems. In this work, a unique Ru^II complex, tris[(5-(4-methylamino-3-aminobenzylamino)-1,10-phenanthroline)] ruthenium(II) hexafluorophosphate [Ru(MAA-phen)₃][PF₆]₂, has been designed and synthesized as a luminescent probe for the detection of NO in aqueous media. The complex itself is almost non-luminescent, but can specifically react with NO under the aerobic conditions to afford its highly luminescent triazole derivative in aqueous media, [Ru(MTA-phen)₃]²⁺ (MTA-phen: methyl-trazolebenzylamino-1,10-phenanthroline), accompanied by a 302-fold increase in luminescence intensity at 598 nm with a 130 nm Stokes shift. The luminescence response of [Ru(MAA-phen)₃]²⁺ to NO is rapid, highly specific without interferences of other reactive oxygen/nitrogen species, and highly stable against the pH changes in the range of pH 4.5–9.5. These features enable [Ru(MAA-phen)₃]²⁺ to be used as a probe for the highly selective and sensitive luminescence detection of NO in weakly acidic, neutral, and weakly basic media.     

Determination of Nickel(II) by CTAB Sensitized Fluorescence Quenching Method of the Derivatives of Calix[4]arene

The fluorescence quenching effect of Ni(2+) on the derivatives of p-tert- butyl-calix[4]arene with o-phenanthroline(TBCP) was studied in cetyltrimethyl- ammonium bromide (CTAB) medium. Ni(2+) reacted with the TBCP to form inclusion complex. The fluorescence quenching was sensitized in CTAB. The linear range of calibration curve for the determination of Ni(2+) was 0.050 μg/mL ~ 1.00 μg/mL. The detection limit estimated (S/N?=?3) was 5.3 ng/mL. It has been applied for the determination of Ni(II) in samples with satisfactory results.     

Peculiarities of crystal structures and magnetic properties of Cu(II) and Ni(II) mixed-ligand complexes on the 1,3-dithiole-2-thione-4,5-dithiolate basis

Mixed-ligand Cu(II) and Ni(II) complexes, [Cu(dmit)(bpy)]₂ (I), [Ni(dmit)(phen)₂] (II) and [Ni(dmit)(phen)₂]·CH₂Cl₂ (III) (dmit=1.3-dithiole-2-thione-4.5-dithiolate, phen=1.10-phenantroline, bpy=2.2′-bipyridine) have been prepared by ligand exchange between phen or bpy and (Bu₄N)₂[M(dmit)₂] (M=Ni, Cu) and characterized by elemental analysis, IR spectroscopy, single-crystal X-ray analysis and by investigation of magnetic and resonance properties. In complex I, the monomeric units form dimers in a head-to-tail arrangement by weak coordination bonds between copper and dithiolate sulfur atoms and π–π interactions between dmit and bpy from neighboring monomers. Dimers in I are further extended into chains by weak Cu–S(thione) contacts. In crystal packing of complex II and III, there exists a weak π–π interaction between two parallel phen molecules of the adjacent complexes. As a consequence, the magnetic and resonance characteristics of copper complex may be described in approximation of exchange-coupled pairs of Cu²⁺ ions with ion spin S=1/2. The nickel complexes are described by isotropic exchange model for single-site spin S=1.     

Ultrasound-assisted fabrication of a novel nickel(II)-bis-pyrazolyl borate two-nuclear discrete nano-structured coordination compound

Ultrasound was used to synthesize nano-structures of [Ni(bpzB)₂]₂(1), a new two-nuclear discrete-coordination compound of divalent nickel with bis-pyrazolyl borate(bpzB). The nanostructure was characterized by scanning electron microscopy, X-ray powder diffraction, infrared, and elemental analysis. The single-crystal X-ray data show that the coordination number of Ni(II) ions is four (Ni1N₄ and Ni2N₄) with square planar geometry. The supramolecular features in these complexes are guided and controlled by weak directional intermolecular interactions. The discrete molecules interact with each other through labile interactions, creating a 3D supramolecular framework.