STUDY ON BINUCLEAR COPPER(I)COMPLEXES III.SYNTHESIS,CHARACTERIZATION AND ELECTROCHEMISTRY OF DICHLORO-TRIS(4-VINYLPYRIDINE)-DICOPPER(I)COMPLEX

Recent years,many novel complexes have been prepared by using hetero-bidentate ligands.However,complexes with such ligands as 4-vinylpyridine which has two different coordinating sites have not been reported,and only a few complexes of Cu(I)have been published^(1-3).The title complex Cu_2(C_5H_4N·CH=CH_2)_3Cl was prepared and characterized by elemental analyses,ICP,IR,and electronic spectra.Its conductivity,oxidation potential and reduction potential were measured.

Synthesis, characterization, and stability of iron (III) complex ions possessing phenanthroline-based ligands

It has previously been demonstrated that phenanthroline-based ligands used to make gold metallotherapuetics have the ability to exhibit cytotoxicity when not coordinated to the metal center. In an effort to help assess the mechanism by which these ligands may cause tumor cell death, iron binding and removal experiments have been considered. The close linkage between cell proliferation and intracellular iron concentrations suggest that iron deprivation strategies may be a mechanism involved in inhibiting tumor cell growth. With the creation of iron (III) phen complexes, the iron binding abilities of three polypyridal ligands [1,10-phenanthroline (phen), 2,9-dimethyl-1, 10-phenanthroline (methylphen), and 2,9-di-sec-butyl-1, 10-phenanthroline (sec-butylphen)] can be tested via a competition reaction with a known iron chelator. Therefore, iron (III) complexes possessing all three ligands were synthesized. Initial mass spectrometric and infrared absorption data indicate that iron (III) tetrachloride complex ions with protonated phen ligands (RphenH+) were formed: [phenH][FeCl4], [methylphenH][FeCl4], [sec-butylphenH][FeCl4]. UV-vis spectroscopy was used to monitor the stability of the complex ions, and it was found that the sec-butylpheniron complex was more stable than the phen and methylphen analogues. This was based on the observation that free ligand was observed immediately upon the addition of EDTA to the [phenH][FeCl4] and [methylphenH] [FeCl4] complex ions.

Kinetics on Thermal Decomposition of Iron(III) Complexes of 1,2-Bis(Imino-4’-Antipyrinyl)Ethane with Varying Counter Anions

A comparative thermal decomposition kinetic investigation on Fe(III) complexes of a antipyrine Schiff base ligand, 1,2-Bis(imino-4’-antipyrinyl)ethane (GA)), with varying counter anions viz. CIO4-, NO3-, SCN-, Cl-, and Br-, has been done by thermogravimetric analysis by using Coats-Redfern equation. The kinetic parameters like activation energy (E), pre-exponential factor (A) and entropy of activation (ΔS) were quantified. On comparing the various kinetic parameters, lower activation energy was observed in second stage as compared to first thermal decomposition stage. The same trend has been observed for pre-exponential factor (A) and entropy of activation (ΔS). The present results show that the starting materials having higher activation energy (E), are more stable than the intermediate products, however;the intermediate products possess well-ordered chemical structure due to their highly negative entropy of activation (ΔS) values. The present investigation proves that the counter anions play an important role on the thermal decomposition kinetics of the complexes.

Synthesis and Characterization of Cr(III) &Fe(II) Bis(2-Methoxybenzylidene)Biphenyl-4,4'-Diamine Complexes

Bis(2-methoxybenzylidene)biphenyl-4,4'-diamine Schiff base was prepared by the reaction of benzidine and O-methoxy benzaldehyde 1:2 reaction. Two complexes of this ligand with Cr(III) and Fe(II) were prepared. All prepared compounds were analysed using elemental analysis, IR, 1H NMR and mass spectroscopy. The formation of proposed structures, including the free ligand and complexes were confirmed.

Syntheses,Crystal Structures and Antibacterial Activities of Complexes [(C_9H_(18)NS_2)_3M(Ⅲ)](M = Sb and Bi)

Two novel complexes,[（C9H18NS2）3Sb（III）]（1） and [（C9H18NS2）3Bi（III）]（2）,were synthesized and characterized by elemental analysis,IR,TG and X-ray single-crystal diffraction.Both 1 and 2 crystallize in the monoclinic system,P21/c space group.The data for 1：a = 1.6964（3）,b = 1.02149（17）,c = 2.5650（3） nm,β = 121.824（8）°,Z = 4,V = 3.7766（10） nm^3,Dc = 1.293 g·cm^-3,F（000） = 1536,μ = 1.082 mm^-1,the final R = 0.0500,wR = 0.1562 and S =1.072.The data for 2：a = 1.6802（9）,b = 1.0256（6）,c = 2.5083（10） nm,β = 121.77（3）°,Z = 4,V = 3.675（3） nm^3,Dc = 1.486 g·cm^-3,F（000） = 1664,μ = 5.159 mm^-1,the final R = 0.0481,wR = 0.1055 and S =1.076.The coordinated geometry of the central M（III） with six sulfur atoms from three ligands is a distorted pentagonal pyramid configuration.The dimer structural system is formed by the weak interactions of M…S and C-H…S between two molecules.The complexes were valued for their antibacterial activities by agar-streak method.It was found that 1 is active against the four test bacterial organisms.

Hydrothermal Syntheses,Crystal Structures,and Characterization of Two Zinc(Ⅱ)Complexes Containing Flexible Bis(benzimidazole)Ligands

Two zinc（II） complexes, namely, [Zn（L1）Cl2]2 （1） and {[Zn（L2）（tbta）]·3H2O}n （2） （L1 = 1,3-bis（2-methylbenzimidazol-1-ylmethyl）benzene, H2tbta = tetrabromoterephthalic acid, L2 = 1,3-bis（2-methylbenzimidazol-1-yl）-2-propanol） have been successfully obtained under hydrothermal conditions. Complex 1 displays binuclear structure which is further extended into a 1D supramolecular chain through π–π stacking. Complex 2 features 2D （4,4） network based on L2/tbta2– double linker. The thermal stability, fluorescence properties and catalytic activities of two complexes for degradation of Methyl orange in a Fenton-like process were discussed.

The Aggregates in LB Films of Schiff base Aluminium (III) Complex

The surface pressure-area (pi -A) isotherm of Schiff base aluminium (III), tris (2-hydroxy-5-nitro-N-dodecyl-benzylideneaminato) aluminium (III) (denoted as Al(TAl2)(3)), on pure water subphase was investigated. The molecular area, 0.48 nm(2), is one-third of expected value that indicated the aggregation took place. The Langmuir-Blodgett (LB) films of Al(TAl2), was transferred and characterized. The AFM image confirmed the formation of aggregates.

Synthesis and Spectral Properties of Mixed-Ligand Complexes of Lanthanide Perchlorate with Bis-(phenylsulfinyl)ethane and Organic Lewis Bases

Six lanthanide complexes with bis(phenylsulfinyl)ethane(bphse) and organic bases(phen: 1,10 phenanthroline and bipy: 2,2'-bipyridine) were synthesized and characterized by elemental analysis, conductance and spectral (IR, UV Visible) data. The complexes were Ln(bphse) 2(bipy)(ClO 4) 3· n H 2O and Ln 2(bphse) 3(phen) 2(ClO 4) 6·H 2O(where Ln=Nd, Eu and Gd; n =0～2). IR spectral data confirmed that the lanthanide ions were coordinated by oxygen atoms from bphse and nitrogen atoms from phen or bipy. Exitation and emission spectra of Eu complexes were measured and discussed.

Synthesis, Characterization, and Reactivity of Amine Bis(phenolato) Cyclopentadienyl Lanthanide Complexes

（C5H5）3Ln（THF）reacted with amine bis（phenol） LH2 [ L = Me2NCH2CH2N {CH2-（2-O-C6H2-But^1-3-Me- 5）}2 ] in a 1：1 molar ratio in THF to generate the amine bis（phenolato） cyclopentadienyl lanthanide complexes LLn（C5H5） （THF）·（THF）,（Ln = La （1）, n =0; Ln = Sm（2）, n = 1） in high yields. Complexes 1 and 2 were fully characterized by elemental analysis, NMR （for 1） and IR spectra, and X-ray structural determination. The crystal data of complex 1 are monoclinic, P21/c space goup, a= 1.1595（1） nm, b = 1.8588（2） nm, c = 1.6647（1） nm, β = 98.490（2）°, V =3.5486（5） nm^3, Z =4, Dc = 1.338 mg· m^3,μ = 1240 mm^-1, F（000）= 1488, R =0.0249, wR = 0.0568. The crystal data of complex 2 are monoclinic, P21/c sp ace goup, a = 0.9692 （1） nm, b = 1.4583 （2） nm, c = 2.8192 （3） nm, = 96.805 （2）°, V = 3.9584 （7） nm^3, Z=4, Dc =1.340 mg · ma, μ = 1.524 mm^-1, F（000）= 1668, R =0.0346, wR =0.0756. The attempts failed to synthesize the amine bis（phenolate） lanthanide alkoxides by the reactions of complexes 1 and 2 with alcohols. The preliminary results revealed that complex 1 can initiate ε-caprolactone polymerization.

Synthesis of a Novel Aromatic Diamino-bridged Bis(β-cyclodextrin) and its Inclusion Complexation with Dyes Molecules

A novel brideed bis（β-cvclodextrin）, 4, 4＇-diaminodiphenyl ether-bfiged-bis （6-aimino-6-deoxv-β-cyclodextrin） 3, has been synthesized and its inclusion complexation behavior with three linear＇guest dyes （AR, NR and MB ） has been investigated by. means of fluorescence spectrometry. The-result obtained demonstrated that the novel bridged bis（β-cyclodextnn） showed much higher affinities towards guest dyes than native β-cyclodextrin.

1, 1'—BIS (BENZYLSELENO) FERROCENE PLATINUM COMPLEX AS HYDROSlLYLATION CATALYST FOR OLEFINS

1, 1'--Bis(benzylseleno)ferrocene and its platinum complex were synthesized. It was found that the platinum complex was efficient catalyst for the hydrosilylation of olefins with triethoxysilane.

Two Three-dimensional Supramolecular Complexes Assembled by 2-Chlorinebenzoic Acid and Bis(imidazol)Ligands:Syntheses,Structures and Fluorescent Properties

Two new three-dimensional supramolecular complexes, namely, [Cd(cba)2(bib)]n(1) and [Zn(cba)2(bib)]2 n(2)(Hcba = 2-chlorinebenzoic acid, bib = 1,4-bis(imidazol-1-yl)-butane)were hydrothermally designed and synthesized. Their structures were determined by elemental analyses, IR spectroscopy, TG, fluorescence spectroscopy, single-crystal and powder X-ray diffraction. Complex 1 exhibits a one-dimensional zigzag chain and complex 2 shows a zero-dimensional structure, which were further extended into three-dimensional supramolecular structures through hydrogen bonds and π-π stacking interactions.

Cu(Ⅱ) and Ni(Ⅱ) Complexes with 5,5'-Bis(2-acylphenyl)diazo-dipyrromethane:Syntheses,Structures and Properties

The reactions of 5,5＇-bis（2-acylphenyl）diazo-dipyrromethane （H2L） with CuSO4 and NiCl2 resulted in the formation of corresponding mononuclear coordination complexes 2 （CuL） and 3 （NIL）. The crystal of complex 2 is of monoclinic system, space group P21 with a = 10.040（5）, b = 11.900（5）, c = 11.170（5） A, β = 93.057（8）°, V = 1332.8（2） A3, Z = 2, C29H28N602Cu, Mr = 556.11, Dc = 1.386 g/cm, F（000） = 578 and/z（MoKa） = 0.857 mm^-1. The crystal of complex 3 belongs to the monoclinic system, space group P21/n with a = 12.0445（6）, b = 17.2101（8）, c = 16.3304（6） A, β = 128.407（2）°, V = 2654.6（2） A3, Z = 4, C29H28N6O2Ni, Mr= 551.28, Dc= 1.380 g/cm, F（000） = 1152 and μ（MoKa） = 0.770 mm^-1. In both complexes, the metal ions are in square-planar geometry by coordinating to two azo N atoms and two deprotonated pyrrole N atoms. Intramolecular Cu…O=C in complex 2 and intermolecular Ni…O=C in complex 3 were found. The UV-Vis spectra and thermal stability of complexes 2 and 3 were also studied.

Synthesis and Structural Characterization of Erbium Complex with Tripodal Ligand, N, N, N′, N′, N″, N″ Hexaisopropyl-2, 2′, 2″-Nitrilotris (2,1-ethoxy) triacetamide (L)

A new tripodal ligand, N, N, N′, N′, N″, N″ hexaisopropyl 2, 2′, 2″ nitrilotris (2,1 ethoxy) triacetamide (L) and its new erbium picrate complex were prepared. The structure of the complex was determined by X ray crystal structure analysis. The result reveals that the Er 3+ is encapsulated by the three arms of the tripodal ligand, and nine coordinated by the bridged head nitrogen atom, all ether oxygen atoms and carbonyl oxygen atoms of the ligand, and two oxygen atoms of the bidentate picrate. The coordination polyhedron is a distorted mono-capped square antiprism.

Synthesis, Crystal Structure, Luminescent Property and DNA-Binding of a Cadmium Complex with 2,4-Bis-oxyacetate-benzoic Acid

A complex [Cd2Na2（BOABA）2（H2O）8]·H2O（1） was synthesized by using 2,4-bisoxyacetate-benzoic acid（H3BOABA） and Cd（OH）2. It was characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. Complex 1 shows a two-dimensional 3-connected rigid plane. The interactions between the ligand and its complex with DNA were studied by Et Br fluorescence probe. Photoluminescent studies indicate that the complex may be excellent candidates for potential photoactive materials.

Studies of Disulfoxide Complexes of Lanthanide Ⅴ.Lanthanide Perchlorate Complexes with Meso-bis(phenylsulfinyl)ethane

Lanthanide perchlorate complexes with meso-bis（phenylsulfinyl）ethane（meso-BPhSE）of type[LnL3-ClO4]（ClO4）2,where Ln=La～Nd,Sin,Gd～Ho,Tm～Lu,have been prepared and characterized by elementalanalysis,electrical conductance,infrared and electronic spectra,magnetic moment measurement and thermalanalysis.Meso-BPhSE acts as a neutral ligand which combines with lanthanide ion through oxygen atom ofdisulfoxide moieties.In all complexes,except that of Ho,meso-BPhSE does not behave as a complete bidentatechelate but does coordinate,at least partially,as a monodentate ligand.For the Ha complex all meso-BPhSEacts as bidentate ones.

The Synthesis and Absorption Character of New Bis (dithiobenzil) nickel Complex NIR Dyes

A series of new NIR dyes bearing 4-(4-morpholinyl) phenyl and substituted phenyl, were synthesized. The maximum absorption wavelengths of these dyes range from 928 nm to 990 nm.

Synthesis and Crystal Structure of a Di-μ_2-phenolic Bridged Binuclear Manganese(Ⅲ) Schiff Base Complex

A new complex [Mn（L）（NCS）]2·0.5CH3CN （H2L = N,N＇-bis（chlorosalicylidene）-1,2-diaminoethane） has been synthesized,and its structure （C70H51Cl8Mn4N13O8S4,Mr = 1833.84） was determined by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system,space group C2/c with a = 25.883（2）,b = 12.3320（13）,c = 13.5951（16） ,β = 112.906（2）,V = 3997.2（7） 3,Z = 2,Dc = 1.524 g/cm3,μ（MoKα） = 1.050mm-1,F（000） = 1852,S = 1.098,the final R = 0.0630 and wR = 0.1847 for 2542 reflections with Ⅰ 〉 2σ（Ⅰ）. The centrosymmetric title complex contains a dimer in which two distorted octahedral Mn（Ⅲ） centers are bridged equatorially by phenolic oxygen of the Schiff base ligand. The units of the complex are linked via weak C-H···N hydrogen bonds,leading to the formation of 1D chains along the b axis. The weak π-π packing interactions and weak intermolecular C（3）-H（3）···N（3） hydrogen bonds stabilize the crystal structure.

Synthesis and Crystal Structure of a New Ternary Mixed Ligand Complex [Cu(ampym)(bapa)Cl](ClO_4) (ampym = 2-Aminopyrimidine, bapa = Bi(3-aminopropyl)amine)

The title complex [Cu（ampym）（bapa）Cl]（ClO4） （C10H22Cl2CuN6O4） was synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. The crystal crystallizes in the orthorhombic system, space group Pna21 with a = 11.9904（12）, b = 15.9796（16）, c = 8.9 i 43（9） A^°, V = 1708.0（3）A^°3 Mr = 424.78, Z = 4, F（000） = 876, Dc = 1.652 g/cm^3, T = 293 K,μ =1 .619 mm^-1 and λ=0.71073 A^°. The structure was refined to R = 0.0240 and wR ： 0.0564 for 2905 observed reflections with I 〉 2σ（I）. Flack = 0.039（12）.