Quantum Chemical Studies on Polydecker Sandwich Compounds with C_3B_2H_5 Ligand

The results of SCF CNDO-CO calculation on polymeric [(η5,μ-2,3-dihydro-1 , 3-di-borolyl)M](M= Cr, Mn, Fe, Co, Ni) indicate that polydecker sandwich compounds with odd valence electrons in each stacking unit (C3B2H5)M have Peierls distorted structures, while those with even valence electrons are favorable to the formation of regular structures. The Band structures show that both LU and HO bands are d-bands for all of the polydecker sandwich compounds studied.

Characterization, XPS and Toxicological Study of Organothallium (III) Compounds with Schiff Base Ligands

Many Organothallium Compounds have been used in medicine, industry and antibacterial activity. Optical properties are among the most fascinating and useful properties of many complexes and have been extensively studied using a variety of optical spectroscopic techniques. A basic understanding of the optical properties and related spectroscopic techniques is essential for characterization about semiconductors, insulators or metal. Optical properties are related to other properties and functionalities (e.g. electronic, magnetic, and thermal) that are of fundamental importance to many technological applications, such as energy conversion, chemical analysis, biomedicine, opto-electronics, communication, and radiation detection. The fundamental importance of Thallium is the ability to accept electrons due to empty d-orbitals and thus establish additional bonds (σ bond and π bond) in chemistry. The Thallium metal, which has outer electronic configuration 6 s2, 6 p1 shows oxidation states of Thallium (III) and Thallium (I). This research paper explains that Thallium (III) and Thallium (I) accepts lone pairs from various bi-dentate tetra-dentate Schiff base ligands due to p-orbital and vacant d-orbital. This research paper explains the Characterization, XPS and Toxicological Study of Or- ganothallium (III) Compounds with Schiff base ligands by physiochemical technique. X-Ray photoelectron spectrogra- phy (XPS) study of Thallium (III) complexes with Schiff Base ligands also reported in this paper. XPS study shows a single symmetrical peak without any splitting in photoelectron peak, which confirms diamagnetic nature of all prepared molecular adducts. All prepared complexes with Schiff base ligands show toxicological effect.

Synthesis,Characterization and Thermal Property of the Aluminum Boroxine-linked Compound with N-aryl Substituted β-Diketiminato Ligand

The boroxine-linked organic aluminum compound LAl[OB（3-C4H3O）]2（μ-O） was accomplished by reacting LAl H2 {L =（Z）-4-[（2,6-diisopropylphenyl）amino]pent-3-en-2-ylidene-2,6-diisopropylaniline} with furan-3-ylboronic acid in good yield.The title compound belongs to the orthorhombic system,space group Pnma with a = 10.9774（15）,b = 19.369（3）,c = 17.362（3） A,V = 3691.5（9） A^3,C37H47 Al B2N2O5,Mr = 648.37,Z = 4,Dc = 1.167 Mg/m^3,μ（Mo Kα） = 0.097 mm^–1,F（000） = 1384,S = 1.000,the final R = 0.0589 and w R = 0.1445 for 9138 observed reflections（I 〉 2σ（I）） and R = 0.0683 and w R = 0.1517 for all data.This compound is an unique example of a spiro-centered aluminum atom,showing the inorganic Al O3B2 ring fused to the organic C3N2 part.It was characterized by 1H NMR,IR,elemental analysis,and single-crystal X-ray structural analysis.Furthermore,the compound was studied by TG analysis as well as DSC.

Synthesis and Crystal Structure of a New Mn_8 Compound with Tripodal Ligand

A new manganese compound [Mn8（tmp）2（Htmp）4（（CH3）3CCO2）4（py）2Cl2]·2py （1·2py, H3tmp = 1,1,1-tri（hydroxymethyl）propane, py = pyramid） has been synthesized and its structure was characterized by IR, elemental analysis and X-ray diffraction. Compound 1 belongs to the triclinic system, space group P1 with a = 13.378（5）, b = 14.334（5）, c = 15.012（6） , α = 107.637（5）, β = 95.635（3）, γ = 92.825（4）°, V = 2720.7（17） 3, Z = 1, C76H124N4O26Cl2Mn8, Mr = 2022.23, Dc = 1.234 Mg/m3, μ = 1.007 mm-1, F（000） = 1052, T = 293（2） K, the final R = 0.0755 and wR = 0.2163 for all 6463 observed reflections （I 〉 2σ（I））. X-ray analysis shows that the core of 1 contains a [Mn8] mixed-valence rod-like unit consisting of six edge-sharing triangles （Mn3）, each of which is bridged by a μ3-oxygen atom.

Syntheses, Characterization and Biological Activity of Coordination Compounds of 3-Hydroxy-2-methyl-4<i>H</i>-pyran-4-one and Its Mixed Ligand Complexes with 1,2-Diaminocyclohexane

Coordination compounds of 3-hydroxy-2-methyl-4H-pyran-4-one with iron(III), cobat(III) and chromium(III) were synthesized with M:L (1:2). Mixed ligand coordination compounds of 3-hydroxy-2-methyl-4H-pyran-4-one and 1,2-diaminocyclohexane using the same metal ions were also synthesized M:L1:L2 (1:1:1) where L1 is 3-hydroxy-2-methyl-4H-pyran-4-one and L2 is 1,2-diaminocyclohexane. The coordination compounds obtained were characterized using electronic and infrared spectral analyses, magnetic susceptibility and percentage metal analysis. They were also evaluated for their cytotoxic and antioxidant activities. The result obtained suggested that octahedral geometry was obtained for all the compounds, as a result of additional two molecules of the solvent coordinated to the metal ions. Both the primary and secondary ligands coordinated in a bidentate fashion. The synthesized compounds exhibited moderate cytotoxicity, although none was as active as the standard. The cobalt(III) mixed ligand complex elicited the highest activity. The synthesized compounds all exhibited good to moderate antioxidant activity.

Syntheses of Coordination Compounds of 2-Amino-3-Methylbutanoic Acid Their Mixed Ligand Complexes and Antibacterial Activities

Coordination compounds of 2-amino-3-methylbutanoic acid were synthesized with chromium(III) and oxovanadium(IV) ions. M:L;1:2. Adducts of these complexes using 1,10-phenantroline and ethylenediamine were further synthesized, M:L, (1:2). These compounds were characterized using electronic, infra-red spectrophotometry, magnetic susceptibility measurement and percentage metal analyses. The zones of inhibition and minimum inhibitory concentrations of the compounds against eight microbes were studied. The results obtained indicated an octahedral geometry for the Cr(III) complexes, indicative of additional coordination of two water molecules. On the other hand a square pyramid geometry was obtained for the binary oxovanadium complex and its 1,10-phenantroline adduct. However, for the oxovanadium ethylenediamine adduct a distorted octahedral geometry was proposed. The result for the antibacterial studies indicated that both mixed ligand complexes of 1,10-phenantroline exhibited good antibacterial activity, and in some cases better activity than the standard, streptomycin.

Organic Carboxylate Ligand Tuned Topological Variations in Three Zn(Ⅱ)Coordination Polymers:Syntheses,Crystal Structures and Photoluminescent Properties

Three new Zn（Ⅱ） coordination polymers, namely [Zn2（suc）2（bib）2]n·nH2 O（1）, [Zn（glu）（bib）]n·4 nH2 O（2）, and [Zn（adp）（bib）]n（3）（bib = 1,4-bis（N-imidazolyl）butane, H2 suc = succinic acid, H2 glu = glutaric acid, H2 adp = adipic acid） have been hydrothermally synthesized and structurally characterized. Compound 1 features a 3D framework with 4-connected hxg-d topological network, compound 2 is comprised of 2D 44-sql-type sheets, and the adjacent 2D sheets are further packed into a 3D supramolecular architecture via intermolecular hydrogenbonding interactions, and compound 3 is a 3D framework with 4-fold interpenetrating dia topology. The structural comparison of these three compounds demonstrates that the topological variations can be well controlled by employing aliphatic dicarboxylate ligands with different spacer lengths. Moreover, the thermal stabilities and photoluminescent properties of them were also studied in detail.

Synthesis, Characterization, and Evaluation of Antitumor Potential in MCF-7 Cells of Ruthenium-Derived Compounds

To synthesize, characterize and evaluate the antitumor potential derived from ruthenium compounds was generated in this study, from the precursor K[RuCl4(bipy)] a route in a simple and reproducible synthesis for a novel compound of coordinating Ru+3 with bipy and L-trip. The spectroscopic characterization in the middle infrared region (FTIR) shows the interactions between Ru-(L-trip), evidenced by the displacement of the carboxylate ion band for higher energies, and also by the displacements of aliphatic amine bands, suggesting that bidentate coordination of the L-trip ligand occurred. Analysis of the results obtained with thermoanalytical techniques showed that the minimum formula of the compound, [RuCl2(bipy)(L-trip)]1/2H2O. Evaluation of the antitumor potential of precursor K[RuCl4(bipy)] showed the toxic effects on MCF-7 cell line, but did not show selectivity and not reached PBMC cells to the same extent. The evaluation of the antitumor potential of the newly synthesized compound, [RuCl2(bipy)(L-trip)], demonstrated that the insertion of an L-tryptophan molecule into the precursor coordination sphere made it selective when compared to PBMC cells, for MCF-7 type tumor cells.

High-capacity Hydrogen Storage on Novel Sandwich-like Binuclear Compounds: N_4-M_2-N_4 (M = Sc and Ti)

With respect to the first principle calculations, we predicted that two pairs of transition metals （e.g., Sc2 and Ti2） can be interbedded between two tetranitrogen rings to form two sandwich-like binuclear complexes respectively （e.g. N4Sc2N4 and NaTi2N4）. These two complexes can adsorb up to eight and ten hydrogen molecules, corresponding to a gravimetric storage capacity of 7.7 and 9.9 wt%, respectively. These sandwich-type complexes proposed in this work are favorable for reversible adsorption and desorption of hydrogen at ambient conditions. The results are helpful for the development of a new class of high-capacity hydrogen-storage media.

Two Novel Complexes Based on N-N Bridged Ligand:Syntheses,Crystal Structures,Fluorescence and Magnetic Property

Two novel coordination compounds,1[Zn4（L1）4（NO3）2（H2O）2]（NO3）2·2H2O and 2[Mn2（L2）2（DMF）（H2O）3]（ClO4）2·DMF（HL1 = N＇-[（1E）-pyridine-2-ylmethylidene]pyrazine-2-carbohydrazide,H2L2 = 2-hydroxy-3-methoxybenzaldehyde（pyrazin-2-ylcarbonyl）hydrazone）,based on the N-N bridged ligands were prepared and structurally characterized.Compound 1represents the[2＊2]molecular squares,in which both N atoms belonging to the N-N bridged ligands are connected to the Zn centers.The emission of compound 1 exhibits a blue shift,which can be assigned to strong electrostatic interaction between Zn^Ⅱ ions and the L1^-1.Compound 2represents a rare phenol-O bridged Mn2^Ⅱ complex.The magnetic investigation indicates weak antiferromagnetic interactions between the Mn^Ⅱ centers.

SYNTHESIS OF ORGANOGERMANE OLIGOMERS VIA LIGAND SUBSTITUTION POLYMERIZATION FROM 1, 4-DIOXANE COMPLEX OF GERMANIUM DICHLORIDE

Some organogermanium oligomers with different side groups were synthesized via ligand substitution polymerization from I, l-dioxane complex of germanium dichloride with different organolithium compounds. The oligomers were isolated through either precipitation from methanol or extraction using toluene with a yield of no less than 50%. The weight average molecular weight (M-w) of the oligomers is ranging from 1.4 x 10(3) to 5.9 x 10(3) depending on the type and alkyl length of the organolithium compounds used.

邻苯二甲酸二异丁酯——新型的ANO2通道开放剂

目的筛选ANO2的特异性配体药物,为医药行业开发靶向ANO2新药提供先导化合物的结构信息。方法构建ANO2过表达的HEK293细胞株,应用共聚焦显微镜-膜片钳全细胞记录模式技术筛选ANO2的特异性配体。结果在胞内外钳制电压100 mV及含1μmol·L^(-1)钙离子电极内液的记录条件下,邻苯二甲酸二异丁酯(diisobutyl phthalate,DIBP)给药前ANO2介导的氯电流密度为(14.67±2.87)pA/pF,给药后ANO2介导的氯电流电导为(28.75±4.05)pA/pF,差异具有统计学意义(P<0.01);钙荧光成像实验结果表明DIBP无调节胞内游离钙信号的作用;在0μmol·L^(-1)钙离子条件下,DIBP对静息状态的ANO2通道不具有直接的激活作用。结论DIBP通过直接作用增强已活化ANO2通道的电导,其作为一种新型的促ANO2通道开放剂为开发靶向ANO2的药物提供结构信息,同时也为研究其他邻苯二甲酸酯类物质的毒理作用提供一定的理论基础。

铜氨配离子结构与稳定性的理论研究

铜(Ⅱ)氨配离子是分析化学教学中配位平衡及配合物的分布特征部分较为经典的配离子之一。现行教材大多只给出了部分铜氨配离子的稳定常数,也并未解释铜氨配离子配位数与稳定性之间的关系。本文使用密度泛函理论,首先通过结构优化给出了铜氨配离子稳定性与配位数和结构的关系,而后进一步通过分析分子内部结构给出了一种回归结构本质的定性解释,既有助于改进教学效果,同时将理论计算应用于分析化学教学过程中,也可增加学生对理论计算的兴趣。

2,2′-联吡啶和去甲基斑蝥酸根桥联双核铜(Ⅱ)配合物的合成、结构表征及抗癌活性的研究

利用二水氯化铜、2 ,2′ 联吡啶和去甲基斑蝥酸钠合成了桥联配体双核铜配合物 [(bipy) (DCA)Cu (DCA) Cu(bipy) (H2 O) ]·3H2 O(式中bipy为 2 ,2′ 联吡啶 ,DCA为去甲基斑蝥酸根 ) .通过元素分析、红外光谱、紫外 -可见光谱和电导对其结构进行了表征 .用X射线单晶衍射测定了该配合物的晶体结构 .配合物经验分子式为Cu2 C3 6H40 N4O14 ,属三斜晶系 ,空间群P1- ,a =1 12 5 1( 2 )nm ,b =1 2 70 7( 3 )nm ,c =1 73 45 ( 4 )nm ,α =94 86( 3 )° ,β =10 7 61( 3 )° ,γ =112 5 0 ( 3 )° ,V =2 12 64 ( 7)nm3 ,μ =1 0 66mm-1,Z =2 ,Dc=1 3 74g/cm3 ,F( 0 0 0 ) =90 8,R =0 0 5 47,wR2 =0 13 5 5 ,GOF =0 815 .配合物中两个铜原子呈六配位的拉长畸变八面体构型 .

配合物[Pd(L)(trp)]Cl·5H_2O(L=phen,5-NO_2phen)的合成、抗癌活性及其与DNA作用研究

合成了两个混合配体配合物 [Pd(phen) (trp) ]Cl·5H2 O (1)和 [Pd(5 NO2 phen) (trp) ]Cl·5H2 O (2 ) (其中phen =1,10 phenanthroline ,5 NO2 phen =5 nitro 1,10 phenanthroline ,trp =L tryptophan) .配合物对肺腺癌细胞AGZY 83a均具有一定的杀伤活性 ,IC50 值分别为 15 8 5 μg/mL和大于 2 93 0 μg/mL .荧光法测定配合物与鱼精DNA的结合常数 (K)分别为 6 36× 10 6和 3 6 4× 10 6.荧光光谱、紫外可见光谱和粘度法证实配合物主要以插入方式与DNA结合 .

一种具有手性联二萘骨架新型TADDOL配体的合成

以3 羟基萘 2 甲酸甲酯4为原料,通过Cu(II)催化的酚氧化偶联、外消旋化合物的拆分和格氏反应等关键步骤,经7步反应以25%的总收率合成了一种具有手性联二萘骨架的新型TADDOL配体12,其光学纯度达到98%.

蛋清肽-Zn(Ⅱ)配合物的制备

为了获得高生物效价的补锌制剂,以蛋清肽为原料,产物中锌的质量分数为测定指标;通过单因素实验和正交实验,确定生成配合物的最优条件,并采用红外光谱法比较了反应前后图谱的变化。结果表明,获得配合物的最优条件为:多肽反应液初始浓度4%,肽锌(ZnCl2)质量比3.5:1,pH为6.0,温度40℃,反应时间40min,最优条件下制得的产物中锌的质量分数为8.25%;红外图谱分析表明两者可能形成了双单齿配位化合物。蛋清肽锌配合物可作为一种新的补锌剂。

一种多孔三维超分子钴配合物的合成与光催化性能

选择一种柔性的N,N′-双(3-吡啶)己二酰胺(L)和邻苯二甲酸(H2BDC)为混合有机配体,利用水热合成技术自组装制备一种新的多孔钴配合物[Co(L)1.5(BDC)(H2O)3]n(1),并通过元素分析、红外光谱和单晶X射线衍射技术表征其晶体结构.实验结果表明:该配合物属于三斜晶系,P1空间群,晶胞参数为a=1.097 87(10)nm,b=1.213 82(11)nm,c=1.429 40(13)nm,α=72.788(2)°,β=75.235(2)°,γ=72.127(2)°,V=1.703 3(3)nm3,Mr=575.43,Z=2,Dcal=1.122g/cm3,μ=0.549 mm-1,F(000)=598,S=1.064,R1=0.054 3,ωR2=0.151 8;配合物中金属钴离子通过双齿的L配体连接形成[Co(L)1.5]2n+n一维链结构,羧酸配体BDC以单齿配位模式悬挂在链的两侧,一维链间通过氢键作用拓展成包含大孔结构的三维超分子网络;该多孔钴配合物在紫外光作用下对有机染料分子亚甲基蓝和刚果红有明显的光催化降解能力.

俄罗斯减压馏分油中硫化物的分离富集及结构鉴定

采用PdCl2配位色谱法对俄罗斯减压馏分油中的硫化物进行了分离和富集。结果表明,PdCl2配位色谱法是分离减压馏分油硫化物的有效手段,不同构型的硫化物在PdCl2配位色谱柱上的保留行为存在很大的差异。运用色谱质谱技术对分离出的硫化物结构进行的鉴定结果表明,俄罗斯减压馏分油中含有烷基环状硫醚、烷基苯并噻吩、烷基二苯并噻吩和烷基萘苯并噻吩等类硫化物。

酰胺基配体构筑的两种铜配合物的组装、结构与催化性能

以N,N'-双(3-吡啶)辛二酰胺(L^1)和对苯二乙酸(H_2pda)为混合有机配体,或者以3-(吡啶-3-氨基甲酰)吡嗪羧酸(L^2)为单一有机配体,在水热条件下自组装制备了两种新的铜配合物[Cu(L^1)(pda)(H_2O)_2]·2H_2O(1)和[Cu(L^2)_2](2),并通过红外光谱、元素分析和X-射线单晶衍射对其结构进行了表征。配合物1是由一维[1D[Cu(L^1)]_(2n)^(2n+)链和μ_2-桥连配位模式的pda^(2-)阴离子连接形成的二维层状结构。配合物2是基于单一配体L^2的一种二维层状结构的聚合物。两种配合物的二维层间通过氢键作用拓展成为三维超分子网络。测试了标题配合物修饰的碳糊电极的电化学行为,而且研究了配合物作为催化剂对多种染料分子的光降解活性。