Schiff碱类芳香性金属配合物的合成及XPS研究

用乙二胺（或丙二胺）缩乙酰丙酮Ｓｃｈｉｆｆ碱三齿配体与咪唑（或苯并咪唑）及金属离子Ｍ（Ⅱ）配位，合成了１２种Ｓｃｈｉｆｆ碱类类芳香金属配合物，对这类配合物的Ｘ射线光电子能谱研究结果表明，配位后，金属离子的２ｐ电子结合能降低，配位Ｎ原子的１ｓ电子结合能增大；这类配全哦分子中的电荷移行径是以Ｌ→Ｍ为主，其配位键以σ键为主。     

K-Pb-Tl-O复合氧化物的合成和电子结构的XPS研究

用熔盐阳极电沉积法合成了导电的复合氧化物K-Pb-Tl-O晶体.这些晶体具有纳米尺寸层状结构.用XPS对其进行了表征,并与相关的化合物进行了比较.实验表明,氧化物中的Pb和Tl都以高价态的单一价态存在,但电子结合能比相应的非导电低价化合物的低.该文用原子外弛豫效应解释了复合氧化物中的Pb和Tl的结合能的反常现象.讨论了它们的价电子结构与导电性的关系.     

稀土富勒烯电子结构的XPS研究

采用Ｘ射线光电子能谱（ＸＰＳ）对富含稀土富勒烯Ｐｒ、Ｇｄ、Ｔｂ、Ｄｙ、Ｅｒ＠Ｃ２ｎ的吡啶提取液的固态沉积膜进行了研究，检测到明确的稀土元素的ＸＰＳ谱峰，表明富勒烯笼内嵌入的稀土元素具有特征的ＸＰＳ谱峰。通过对谱峰的分析，发现稀土富勒烯具有较为稳定的结构。嵌入的Ｐｒ、Ｇｄ、Ｔｂ、Ｄｙ、Ｅｒ等稀土元素与富勒烯球笼间存在电子的迁移。     

Schiff碱,咪唑金属配合物合成及抗癌活性的荧光筛选研究

本文报道了一类新的Ｓｃｈｉｆｆ碱和唑的混合型金属配合物（即水杨醛缩甘氨酸，咪唑金属配合物和２．４－二羟基苯甲醛缩丙氨酸，咪唑金属配合物）的合成，以及用溴化乙锭荧光分析法对这类配合物与ＤＮＡ相互作用的研究。结果表明，其中金属镍配合物与ＤＮＡ的作用效明显，可作为具有抗癌作用的药物进行深入研究。     

系列过渡金属与三角架多咪唑配合物的合成、结构及表征

以三氨乙基胺和N－甲基咪唑醛为原料合成了三角架多咪唑配体((min)₃tren)，并合成了五个过渡金属配合物：[Zn(min)₃tren](ClO₄)₂1， [Cu(min)₃tren](ClO₄)₂2, [Ni(min)₃tren](ClO₄)₂3, [Co(min)₃tren](ClO₄)₂4, and [Mn(min)₃tren](ClO₄)₂CH₃CN 5，通过元素分析，摩尔电导率，红外和电子光谱确定了化合物的组成。对配合物4和5进行了晶体结构测定。结果表明，在这两个化合物中金属原子均处于扭曲的八面体配位环境，分别与三个亚胺氮原子和三个咪唑氮原子配位。配合物4和5的电化学研究表明在乙腈溶液中，有[Co-O₂]^n-和[Mn-O₂]^n-存在，认为4和5是很好的超氧化物清除剂。     

酰基吡唑啉酮双席夫碱配合物的电子结构、成键性与生物活性

The electronic structures of N,N′-bis[(1-phenyl-3-methyl-5-oxo-4-pyrazolinyl) α-furylmethylidyne]ethylendii- mine (and -o-phenylendiimine), and their complexes of transition metals M (M=Ni, Cu, Co, Pd, Pt) have been calculated by B3LYP method of DFT. Their geometries and bonding characters are discussed, and the relationship between their bioactivities and electronic structures are also discussed from the calculated results of electronic populations and frontier orbital energies.     

稀土与L-谷氨酰胺配合物的电子能谱研究

合成了通式为LnL_3Cl_3·2H_2O(Ln=Eu,Tb,Ho,Tm;L=L-谷氨酰胺)的固体配合物。用XPS辅以元素分析、热分析及IR光谱研究了配合物的组成及性质。观察到配合物中O_(1a)、Ln_(3d)、Ln_(4d)和Cl_(2p)结合能的变化,并发现Eu配合物Eu_(3d)谱峰的伴峰结构,讨论了伴峰产生的机理。     

过渡金属氨基酸席夫碱配合物的合成

合成了6个过渡金属氨基酸席夫碱配合物——L-酪氨酸缩水杨醛合铬(钼),L-赖氨酸缩水杨醛合铬(钼),DL-α-丙氨酸缩水杨醛合铬(钼),其结构经UV,IR和元素分析表征。UV测定结果表明,配合物均可与DNA发生插入作用。     

席夫碱及其金属配合物的合成及生物活性研究进展

席夫碱及其金属配合物具有独特的抗菌、抗肿瘤和抗氧化等生物活性.为筛选高效低毒的药物,人们合成了大量不同类型的席夫碱及其金属配合物并对其生物活性进行了研究.本文综述了近年来席夫碱及其金属配合物的合成,以及在抗菌、抗氧化、抗肿瘤等方面生物活性的研究进展,并为进一步研究其在医药领域的应用提供了信息支持.     

过渡金属席夫碱配合物的稳定性及其杀菌活性

在25±0.1℃,I=0.1 mol·L^-1 KNO₃条件下,应用pH法测定了甲酰基甲酸缩氨基硫脲(A配体,缩写H₂FFTSC),甘氨酰甘氨酸(B配体,缩写HGG)的质子化常数,它们与锰(Ⅱ)、钴(Ⅱ)、镍(Ⅱ)、铜(Ⅱ)和锌(Ⅱ)的二元配合物以及过渡金属(Ⅱ)-甲酰基甲酸缩氨基硫脲-甘氨酰甘氨酸三元配合物稳定常数,讨论了过渡金属席夫碱配合物的杀菌活性与其稳定性之间的关系,对杀菌机理提出了一些看法。     

Synthesis,Characterization and Antifungal Activity of Metal Complexes of 2-(5-((2-Chlorophenyl)Diazenyl)-2-Hydroxybenzylidene) Hydrazinecarbothioamide

Abstract

New metal complexes of Co(II), Cu(II), Ni(II), Zn(II), Mn(II), Fe(III), Ru(III), UO₂(II), and VO(II) with the Schiff base, 2-(5-((2-chlorophenyl)diazenyl)-2-hydroxy- benzylidene) hydrazine-carbothioamide (H₂L) have been prepared and characterized by elemental and thermal analyses, FT-IR, UV–Vis, mass spectra, ¹H-NMR, and ESR as well as conductivity and magnetic moments measurements. The IR spectra showed that the ligand acts as neutral tridentate, neutral bidentate or monobasic tridentate ligand. The geometries of metal complexes were either octahedral or square pyramidal. The ESR spectra of the solid copper(II) complexes indicated an axial symmetry type of a d_(x2-y2) ground state with considerably ionic or covalent environment. The effect of the presence of an azo group on the biological activity of the ligand was investigated. The ligand and its complexes are biologically inactive due to the presence of azo group.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the related elements to view the free supplemental file.     

8-羟基喹啉银(铂)金属配合物电子光谱与非线性光学性质

运用密度泛函理论B3LYP方法对8-羟基喹啉(银、铂)(AgQ、PtQ₂)金属配合物及其衍生物的非线性光学性质进行理论计算研究. 结果表明: 引入取代基使铂配合物的最强吸收波长产生较大红移. 最低能量跃迁吸收来自最高占据分子轨道(HOMO)到最低空分子轨道(LUMO)的d→π^*和π→π^*跃迁, 属于金属配体电荷转移(MLCT)与配体配体电荷转移(LLCT). 金属银和铂掺杂8-羟基喹啉使其三阶非线性光学系数γ值明显增大, 并且在配合物上引入―Ph, ―PhOCH₃, ―PhF₂, ―PhF₅基团将进一步增大γ值. 引入基团的供电子性越强, γ值增大的幅度越大, 引入基团的吸电子性越强, γ值增大的幅度越小.     

Synthesis and Crystal Structure of 5-Methyl- 2-phenyl-4-[（2-p-bromophenylamino）-furylmethylene]-3（2H）-one

A novel 4-heterocyclic acylpyrazolone-based Schiff base compound 5-methyl- 2-phenyl-4-[（2-p-bromophenylamino）-furylmethylene]-3（2H）-one （C21H16N3O2Br） has been synthesized by the reaction of 1-phenyl-3-methyl-4-（α-furoyl）-pyrazolone-5 （HPMαFP） and p-bromoaniline. Elemental analysis, IR spectra and X-ray single-crystal diffraction were carded out to determine the composition and crystal structure of the compound. Crystal data： triclinic system, space group P1^-, a = 9.0936（3）, b = 9.8067（4）, c = 11.6863（4） A, α = 102.512（10）, β = 90.9630（10）, γ = 114.327（10）°, Mr= 422.28, Z= 2, F（000） = 428.0, V= 920.46（11）A^3, Dc = 1.524 g/cm^3,μ = 2.254mm^-1, R = 0.0476 and wR = 0.1318 for 9389 independent reflections （Rint = 0.0122） and 3281 observed reflections （I 〉 2σ（I））. Structural analysis indicates that the compound exists in an amine-one form.     

Synthesis and Crystal Structure of (E)2-(3'-Bromo-5'-chloro-salicylidene amino)-4-methyl Pyridine

A new Schiff base compound,2-bromo-4-chloro-6-[(4-methylpyridin-2-ylimino)me-thyl]phenol(C13H10BrClN2O),has been synthesized by the condensation of equimolar 3-bromo-5-chlorosalicylaldehyde and 4-methylpyridin-2-ylamine in a methanol solution.The compound Was characterized by elemental analysis,IR spectra,and single-crystal X-ray diffraction.The crystal belongs to the monoclinic system,space group P21 with a=6.048(3),b=14.063(7),c=7.623(4)(A),β=97.703(7)°,Z=2,V=642.5(6)(A)3,Dc=1.683 g/cm3,Mr=325.59,λ(MoKa)=0.71073(A),μ=3.395 mm-1,F(000)=324,R=0.0370 and wR=0.0662.A total of 3879 reflections were collected,of which 1970 with,I＞2σ(I)were observed.As expected.the molecule adopts a trans configuration about the C=N double bond.The benzene and pyridine rings are nearly coplanar(mean deviation from the combined plane is 0.031(3)(A)),with their dihedral angle of 3.3(3)°.The preliminary biological tests show that the compound has excellent antibacterial activities.     

LnCu_2O_4(Ln=Gd,Nd)电子结构的XPS研究

用 XPS测定了 LnCu2O4(Ln=Gd, Nd)的内层和价层电子能谱,观察到 LnCu2O4中稀土金属的 3d电子结合能比相应的稀土金属简单氧化物的 3d结合能低 0.8～ 0.9 eV,而 Cu的 2p电子结合能比 CuO的高 0.4～ 0.5 eV,因此推断在 LnCu2O4的 Ln－ O－ Cu链中存在 Cu→ O→ Ln电荷转移 .XPS分析还表明 LnCu2O4的 Cu原子上有较低的电荷密度,但不存在混合价态 .此外,通过比较价电子能谱,发现 NdCu2O4的 Ln 4f Cu 3d O 2p价带中心比 GdCu2O4的价带中心向 Fermi能级移近了 3.4 eV,而且 NdCu2O4的价带谱更窄 .     

Electronic Structure of Cu(II) Complexes with N,N′-Disalicylidene-1,2-cyclohexanediamine and N,N′-Disalicylidenetrimethylenediamine

Summary.  The electronic absorption and X-ray photoelectron spectra of N,N′-disalicylidenetrimethylenediaminatocopper(II) ([Cu(saltn)]) and N,N′-disalicylidene-trans-1,2-cyclohexanediaminatocopper(II) ([Cu(salchx)]) were measured. From these results and from informations derived from MO calculations the electronic structure of the complexes was clarified. Each electronic absorption band which can be assigned to the ππ^ast; or ML/LMCT transition of [Cu(saltn)] or [Cu(salchx)] observed in the wavelength region of 450–200 nm appears at the almost same frequency as the corresponding band of N,N′-disalicylideneethylenediaminatocopper(II) ([Cu(salen)]) in solution. The LLCT bands (the intramolecular CT band between two π-electronic systems separated by saturated hydrocarbon chains such as ) also appear at nearly the same positions (ca. 245 nm) for [Cu(salchx)], [Cu(saltn)], and [Cu(salen)]. The locations of the dd transition and the intensity of the ML/LMCT transition of [Cu(saltn)] are significantly different from those of [Cu(salen)] and [Cu(salchx)]. These differences may arise from the strengths of the interaction between metal and ligand. Received August 21, 2001. Accepted (revised) October 20, 2001     

一水合(E)-N'-(5-氯-2-羟基苯亚甲基)-2-(8-羟基喹啉基)-乙酰肼Schiff碱的合成及其晶体结构

在甲醇溶液中,5-氯水杨醛和8-羟基喹啉乙酰肼经缩合反应合成了新化合物--一水合(E)-N'-(5-氯-2-羟基苯亚甲基)-2-(8-羟基喹啉基)-乙酰肼Schiff碱(1),其结构经1H NMR,IR,元素分析和X-射线单晶衍射表征.1属正交晶系,P2_12_12_1空间群,晶胞参数:a=4.748(5) (A),b=15.818(14) (A),c=22.802(2) (A),α=β=γ=90.00 °,V=1 712.0(3) (A)~3,Z=4,Dc=1.450 g·cm~(-3),μ=0.253 mm~(-1),F(000) =776,R_1=0.072 5,wR_2=0.102.1通过氢键相互作用,连接成一维无限链结构.     

Novel Isatin-Schiff Base Cu (II) and Ni(II) Complexes. X-ray Crystal Structure of Bis[3-(4-hexylphenylimino)-1H-indol-2(3H)-one]-dichlorocopper(II) Complex

Schiff bases of isatin were reported to possess antibacterial, antifungal, antiviral, anti-HIV, antiprotozoal, and anthelmintic activities1. They also exhibit significantanticonvulsant activity, apart from other pharmacological properties2. Conductingsubs…     

The Crystal Structure of Binuclear Metal Complexes of 7-Azaindole: Cu2 (CH3CO2)2 (C7H5N2)2(C7H6N2)2 AND Ni2(C7H5N2)4.2DMF

The crystal and molecular structures have been determined by single-crystal X-ray methods for the binuclear metal ions (II) complexes of 7-azaindole (1H-pyrrolo [2,3-b] pyridine, C₇H₆N₂ denoted by HL), Cu₂(CH₃CO₂)₂.·L₂(HL)₂ and Ni₂L₄.2DMF. The dark green crystal of Cu₂(CH₃CO₂)₂L₂(HL)₂ was found to crystallize in the monoclinic space group P 2₁/n with a = 9.566(2), b = 12.752(2), c = 12.852(4) Å, β = 99.23(3)⁰, V = 1547 Å, Z = 2, the final R = 0.062 and Rw = 0.053 for 1488 observations from 2722 unique reflections. The Cu-Cu distance is 2.747(2), Cu-N (L^?, bridge) is 1.966(7), Cu-N (HL, axial) is 2.229(8), and Cu-O is 2.031(6)Å. The red crystal of Ni₂L₄.2DMF was was found to crystallize in the triclinic space group \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm P \bar 1} $$\end{document} with a = 8.907(5), b = 9.462(2), c = 10.217(2) Å, α = 90.48(2), β = 91.09(3), γ = 110.69(3)⁰, V =805 ų, Z = 1, the final R = 0.063 and Rw = 0.069 for 1489 observations from 2834 unique reflections. The Ni-Ni distance is 2.594(2), Ni-N is 1.905(7) Å. These two molecules lie on crystllographic inversion centers and exhibit ligand disorder.