Two novel Cu(Ⅰ)complexes based on diimide and bisphosphine ligands:synthesis,crystal structure and spectroscopic properties

Two Cu(Ⅰ)complexes[Cu(Bphen)(dppBz)]ClO_(4)·2CH_(3)OH(1)and[Cu_(2)(Bphen)_(2)(dpppda)]BF_(4)(2){Bphen=4,7-diphenyl-1,10-phenanthroline,dppBz=1,2-Bis(diphenylphosphino)benzene,dpppda=N1,N1,N4,N4-tetrakis[(diphenylphosphino)methyl]-1,4-benzenediamin}were synthesized using a one-pot method.X-ray crystallography was used to elucidate their crystal structures and photophysical properties.A series of characterization tests including elemental analysis,NMR,FT-IR,UV-Vis absorption spectroscopy,fluorescence spectroscopy,thermal gravimetric analysis and terahertz time-domain spectroscopy(THz-TDS)were used to further investigate their properties.The results show that complex 1 structure is mononuclear containing two solvent molecules per unit cell,while complex 2 structure is binuclear containing two metal centers per unit cell.According to photophysical properties and density functional theory(DFT)calculations,their luminescence properties can be attributed to metal-to-ligand charge transfer(MLCT).Both complexes have a unique stability,which is confirmed by thermal gravimetric analysis.

Synthesis and Crystal Structure of a Novel Binuclear Copper(Ⅱ) Complex, [Cu(paba)Cl]

A novel binuclear Cu（Ⅱ） complex [Cu（paba）Cl] （pabaH = 2-（2-pyridylmethylimine）benzenesulfonic acid） has been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. The crystal of the title complex crystallizes in a monoclinic system, space group P21/n, with a = 6.8165（7）, b = 15.3073（16）, c = 12.3795（13） A^°, β= 95.0160（10）°, V= 1286.8（2） A^°^3, Mr = 360.26, Dc= 1.860 g/cm^3,μ = 2.074 mm^-1, F（000） = 724, Z = 4, the final R = 0.0252 and wR = 0.0675 for 2395 observed reflections with I 〉 20（I）. The title complex is centrosymmetric and a pair of chlorides act as μ2-bridges to link two Cu（Ⅱ） ions forming a binuclear complex. Every Cu（Ⅱ） ion is five-coordinated by pyridyl N, imine N and sulfonate O atoms of the tridentate paba ligand as well as two bridging Cl^-, constructing the distorted square-pyramidal geometry. In the structure extensive hydrogen bonds and weak π-π stacking stabilize the solid structures, through which the complex builds its 3-dimensional supramolecular structure.

A Novel Binuclear Cu(Ⅱ) Complex with Nitroxide Radicals Exhibiting Ferromagnetic Interactions

A new binuclear Cu（Ⅱ） complex with nitronyl nitroxide radicals [Cu（NIT3Py）2Cl2]2（NIT3Py = 2-（3＇-pyridinyl）-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide） has been synthesized and structurally characterized by X-ray diffraction analysis.It crystallizes in monoclinic,space group C2/c with a = 38.483（4）,b = 7.2450（8）,c = 27.559（3） ,β = 134.0180（10）°,V = 5525.6（10） 3,C48H64Cl4Cu2N12O8,Mr = 1206.00,Z = 4,Dc = 1.450 g/cm3,μ（MoKα） = 1.025 mm-1,F（000） = 2504,S = 1.066,the final R = 0.0471 and wR = 0.1121 for 3286 observed reflections（I 2σ（I））.The title complex consists of centrosymmetric dinuclear units [Cu（NIT3Py）2Cl2]2,in which the copper ions are square-pyramidally coordinated by two pyridyl nitrogen atoms of two radical ligands and three chlorine anions,two of which bridge the copper ions.The magnetic measurements show ferromagnetic interactions between the copper ions and the radical ligands.

Syntheses and Magnetic Properties of Cu（Ⅱ）－RE（Ⅲ） Heterobinuclear Complexes with N，N′－Bis（3－carboxyisalicylidene）－trimethylenediamine

ine heterobinuclear complexes of Cu (Ⅱ)-RE (Ⅲ) with N, N′-bis-(3-car-boxylsalicylidene ) trimetliylenediamine (TS) were syntliesized and characterized bymeans of elemental analyses, molar conductivity, thermogravimetry,IR and elec-tronic spectra. The measurements of variable-temperature magnetic susceptibilitysliow that there exists only a very weak antiferromagnetic spin exchange interactionbetween the ions of Cut(Ⅱ) and RE(Ⅲ) in CuRETSCI . 3H_2O.

Synthesis and Crystal Structure of a Binuclear Gadolinium（Ⅲ） Complex Bridged by Cucurbit[6]uril

A new cucurbit[6]uril bridsed binuclear complex {[Gd（H2O）6]2[Q6（H2O）]}C16·4H2O, where Q6 represents cucurbit[6]uril, has been synthesized and characterized by X-ray diffraction. The crystal structure shows that the complex has an extended cucurbit[6]uril-bridged structure consisting of two gadolinium（Ⅲ） ions, in which each gadolinium（Ⅲ） ion is coordinated with two neighboring carbonylic oxygen atoms of Q6 and six oxygen atoms of water molecules that leans toward one side of the portal. One disordered guest water molecule resides in the Q6 molecule cavity and occupies two different positions. Hydrogen bonds assemble the complcx to threedimensional supramolecular structure.

SYNTHEIS, SITUCTURE AND CHARACTERIZATION OF BINUCLEAR Cu(II)COMPLEX[Cu(C_6H_5COO)_2(C_5H_6N_2)]_2.(C_4 H_8O)_2

At room temperature,dibenzoyl peroxide undergoes oxidative addition on metallic Copper Powder and 2-aminopyridine in a solvent(acetone and tetrahydrofuran), which affords the product as a binuclear Cu(II)complex [Cu (C5 H5 COO)2(C5 H5 N2)]2. (C4 H5 O)2. The structure of the complex was characterized by elemental analyses. IR spectra, TG-DTA. The structure of the compound has been solved by direct method and Fourier synthesis, and refined by block-diagonal and full matrix least-squares method to a final R of 0.04329 for 3671 independent reflection of I>e(I). The crystals are triclinic, C46H45N4O10Cu2.Z=1, Mr=943.93, space group P-1, with cell parameters, a=10.806(1); b=11.169(3);c=11.729(2)A; α=71.99(2),β=89.38(1)°; γ=81.37(1); V=1330.1A3; Dc=1.172g.cm-3;μ=8.5cm-1. The copper(II) ion is coordinated by four bridging bidentate benzoate and two 2-aminopyridine to form dimeric molecules.

PREPARATION, CHARACTERIZATION AND ELECTROCHEMISTRY OF BINUCLEAR COPPER(I) COMPLEXES Cu_2(dppm)Cl_2 AND Cu_2(dppe)Cl_2

Two binuclear copper(I) complexes with novel structures and novel bonding,Cu_2(Ph_2PCH_2PPh_2)Cl_2 (Ph_2PCH_2PPh_2=dppm) and Cu_2(Ph_2P-CH_2CH_2PPh_2)Cl_2 (Ph_2PCH_2CH_2PPh_2=dppe), were prepared and characterized through elemental analyses, ICP, IR(4000-200 cm^(-1), CsI disc.), ^(31)P-NMR spectra. Their electronic conductivities, oxidation and reduction potentials were measured. Preliminary studies show that both of the two complexes have chlorobridging and phosphorus-bridging structures.

Ab Initio Molecular Orbital Calculation on Dinuclear Gold(Ⅰ) Complexes──Metal-Metal Interaction and Electronic Structure of Binuclear Gold(Ⅰ) Complexes with Bridging Bidentate Ligands

The electronic structure and electronic absorption spectra of binuclear Au(Ⅰ) complexes with bidentate phophines and a bidentate ylid ligand have been studied using quasirelativistic pseudopotential ab initio calculations at the HF and MP2 levels by the LANL2DZ basis sets. The electronic properties of the spectral transition and Au(Ⅰ)—Au(Ⅰ) interaction were also discussed.

FERROMAGNETIC INTERACTION BETWEEN GADOLINIUM（Ⅲ） AND COPPER （Ⅱ）IONS IN N，N＇－BIS（2－AMINOPROPYL）OXAMIDO COPPER（Ⅱ） BRIDGED BINUCLEAR Gd（Ⅲ）－Cu（Ⅱ） COMPLEX

The heterobinuclear complex of formula Cu (oxap )Gd(phen)2 (CIO4 )3 has been synthesized, where oxap denotes the N, N'-bis (2-aminopropyl )oxamido dianion and phen represents 1,10-phenanthroline. The complex was characterized with ESR and variable temperature magnetic susceptibility (4- 300K). The least-squares fit of the experimental sosceptibilities yielded J=2. 25cm-1. The observed Gd (Ⅲ)-Cu (Ⅱ) coupling is ferromagnetic.One Plausible mechanism that can cause a ferromagnetic coupling between Gd(Ⅱ) and Cu (Ⅱ) is discussed in terms of spin-polarization.

Synthesis, structures, and properties of two new binuclear complexes based on carboxyl-substituted nitronyl nitroxide: [M₂(NITpBA)₄(H₂O)₂] (M = Zn and Cu)

Two new binuclear complexes, [M2(μ-NITpBA)4(H2O)2] (M = Zn 1 and Cu 2) [where NIpBA =?2-(4-carboxyl-phenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl-3-oxide], were stylized and characterized. Magnetic susceptibility measurements revealed antiferromagnetic exchange interactions in two complexes.

Crystal Structure and Molecular Structure of Binuclear Copper(Ⅱ) Complex, [Cu (C_5H_5NO) (C_6H_5COO)_2]_2

At room temperature, dibenzoyl peroxide and pyridine N-oxide reacted with metallic copper powder in a mixed solvent(dichloromethane, trichloromethane and tetrahydrofuran), resulting in a binuclear copper(Ⅱ) complex. [Cu (C_5H_5NO)-(C_6H_5COO)_2]_2. The structure of the complex was characterized by elemental analyses.IR spectra and X-ray single crystal analysis. The crystal is triclinic, space group P1,with cell parameters . a= 9. 262(4) ,b= 10. 697(2) , c=10. 881 (3 )A , a=59. 60( 2 ),β= 74. 83 ( 3 ) .Y = 72. 80 ( 2 )°. V= 880. 0 A￣3 . D_c = 1 . 5 20 g/cm￣3 . Z = 1 . μ= 1 2. 7 cm-1, R=0. 044 ,R_w=0. 048 for 3477 reflections with I>3σ(I), M_r=805. 78. Each copper(Ⅱ) atom is coordinated by four bridging bidentate benzoate ligands and one pyridine M-oxide.

Solid State Synthesis and Structural Characterization of Binuclear Cu(I) SbPh 3 Complex 〔Cu(SbPh 3) 2I〕 2

Dimeric complex 〔Cu(SbPh 3) 2I〕 2 has been synthesized by a solid state reaction at a low heating temperature and its crystal structure has been analyzed by X ray crystallography. The crystal is monoclinic, space group P2 1/a (#14), a = 20 436(5), b=14.125(3), c=24.683(3) , β=110.67(1)°, Z=4, V =6666(2) 3; C 72 H 60 Sb 4I 2Cu 2, M r = 1792, D c = 1.787 g·cm -3 , μ (Mo Kα ) = 31.88 cm -1 , F(000)=3440, R= 0.038 and R w= 0.043 for 5632 observed reflections ( I≥3.0σ(I) ) and 361 refined parameters. The result reveals the copper and the bridging iodide atoms form an approximately planar rhomboid array. Effects of the bulkiness of the ligands upon the structures of the analogous complexes are discussed.\;

Effects of binuclear copper(Ⅱ)threonine complex on blood glucose, lipids and protection of the hearts and kidneys in diabetic mice

Aim To study the effects of binuclear copper （Ⅱ） threonine complex （Cu2 （Thr）4） as analogue of superoxide dismutase （SOD） on blood glucose, blood lipids and vessels of hearts and kidneys in diabetic mice. Methods Diabetic mouse model was established by intraperitioneal injection of alloxan. Low, middle, and high doses of Cu2（Thr）4 at 0.002%, 0.02% and 0.1% were given respectively to diabetic mice following lavage. The fasting blood glucose was determined after the diabetic mice were given Cu2 （Thr）4 for 0, 30, and 45 d. The diabetic mice were killed on the 45th day. Then glycosylated hemoglobin （HbAlc） and blood lipids were assayed, and pathologic changes in hearts and kidneys stained with HE were observed. Results Compared with the control group in which the diabetic mice were given distilled water, the value of blood glucose reduced significantly in middle dose group （P 〈 0.01 ）, followed by that in low dose group （P 〈 0.05）. TC level reduced markedly and HDL level increased significantly in all three treatment groups （P 〈 0.05）. Especially in middle dose group, cardiac muscle fibers were neatly arranged, nucleus and cytoplasm well distributed, glomeruli showing normal structure, cells well distributed and staining being normal. Conclusion Cu2 （Thr）4 reduces blood glucose, regulates blood lipids, and play protective action on the vessels of hearts and kidneys in diabetic mice. The effects of it in middle dose were better than those of other doses.

Characterization and performance of Cu/ZnO/Al_2O_3 catalysts prepared via decomposition of M(Cu,Zn)-ammonia complexes under sub-atmospheric pressure for methanol synthesis from H_2 and CO_2

Methanol synthesis from hydrogenation of CO2 is investigated over Cu/ZnO/Al2O3 catalysts prepared by decomposition of M（Cu,Zn）-ammonia complexes （DMAC） at various temperatures.The catalysts were characterized in detail,including X-ray diffraction,N2 adsorption-desorption,N2O chemisorption,temperature-programmed reduction and evolved gas analyses.The influences of DMAC temperature,reaction temperature and specific Cu surface area on catalytic performance are investigated.It is considered that the aurichalcite phase in the precursor plays a key role in improving the physiochemical properties and activities of the final catalysts.The catalyst from rich-aurichalcite precursor exhibits large specific Cu surface area and high space time yield of methanol （212 g/（Lcat·h）;T=513 K,p=3MPa,SV=12000 h-1）.

Electrocatalytic oxidation of methanol at platinum electrode modified with Eu-Fe cyanide-bridged binuclear complexes

The electrocatalytic oxidation of methanol at the platinum electrode modified with Eu-Fe cyanide-bridged binuclear complexes (Eu-Fe film) was investigated for the first time by cyclic voltammetry.Compared with the bare platinum electrode,the results showed that the modified electrode had excellent electrocatalytic activity for the oxidation of methanol;the oxidation peak potential shifted more negatively and the peak current increased about twenty times.The electrooxidation of methanol at the modified elect...

Synthesis and Crystal Structure of Bridging Complex [Cu_2(bipy)_2·OAc·Cl·OH]·TsTausH·3H_2O

The title complex [Cu2(bipy)2OAcClOH]TsTausH3H2O(C31H37Cl- Cu2N5O11S2) has been synthesized by the reaction of 2,2?bipyridine(bipy), N-P-tolysulfony taurine (TsTausH) and copper acetate in water-ethanol solution, and its crystal structure was determined by X-ray diffraction method. The crystal belongs to triclinic, space group P with a = 0.74485(14), b = 1.6094(3), c = 1.7472(3) nm, a = 114.662(4), b = 99.997(4), g = 93.218(4), V = 1.8551(6) nm3, Mr = 882.31, Z = 2, Dc = 1.580 g/cm3, m = 1.395 mm-1 and F(000) = 906. The complex is a binuclear copper compound, and the two copper ions nearly have the same coordination environment. There exists MM bond in the complex. The distance of Cu(1)Cu(2) is 0.29747(7) nm. The two ions form two distorted octahedral geometries.

Synthesis and Characterization of Two Binuclear Macrocyclic Zinc(Ⅱ) Complexes by Anion Exchange

Two macrocyclic zinc（Ⅱ） complexes {[ZnL（VO3）2]·0.33H2O}n（1） and [ZnL（H2O）2][Ni（CN）4]（2）（L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane） have been obtained from the reactions of [ZnL]（ClO4）2 with NH4VO3 and K2[Ni（CN）4], respectively, and structurally characterized by elemental analysis, IR, XRPD, TG and X-ray diffraction. Single-crystal X-ray diffraction analyses indicated that the Zn（Ⅱ） atom lies on an inversion center and is octahedrally coordinated by four nitrogen atoms of the tetradentate macrocyclic ligand in the equatorial plane and two oxygen atoms of [VO4] tetrahedra in the axial positions in 1, and two oxygen atoms of two water molecules in 2. Complex 1 shows a three-dimensional structure, which is constructed by the links of [VO3]nn- chains with [ZnL]2＋, forming one-dimensional channels occupied by guest water molecules. The monomers of [ZnL（H2O）2]2＋ and [Ni（CN）4]2- are connected through the intermolecular hydrogen bonds to form a two-dimensional sheet in complex 2.

Hydrothermal Synthesis, Crystal Structure and Fluorescence Properties of a Three-dimensional Triply-bridged Binuclear Zinc(Ⅱ) Complex [Zn_2(Mba)_3(Phen)_2EtOH)]·ClO_4

The novel complex [Zn2（Mba）3（Phen）2EtOH）]·ClO4 （Hrnba = methoxybenzoic acid, Phen = 1,10-phenanthroline, EtOH = ethanol） was synthesized by hydrothermal reactions, and its structure was determined by X-ray diffraction. The crystal belongs to the triclinic system, space group Pi with a = 1.15362（1）, b = 1.3655（3）, c = 1.61451（1） nm, α= 72.842（2）, β = 83.259（3）, y = 72.083（2）°, V = 2.3112（6） nm3, Z = 2,μ（MoKa） = 11.71 cm-1, F（000） = 1120, R = 0.0552 and wR = 0.1157 （I 〉 2σ（I））. The two centric zinc（H） ions in the complex locate in a distorted octahedral coordination geometry and a distorted trigonal bipyramid coordination geometry, respectively. Two bridging bidentate carboxyl groups and a μ2-O carboxyl group from three methoxybenzoic acids act as the bridge to link two Zn（Ⅱ） ions. The asymmetric units are connected by π-π packing interactions between aromatic rings to form a three-dimensional supramolecular network. The experimental results show a good fluorescence property for the complex.

复杂多组元Cu-Cr-Zr-Ni-Si-Co-Zn合金时效析出动力学研究

Cu-Cr-Zr及Cu-Ni-Si合金均为性能优异的引线框架材料,但二者性能均存在局限性。Cu-Cr-Zr合金具有优异的导电性能,但其强度偏低;Cu-Ni-Si合金具有极高的强度,但其导电性能一般。如果结合二者的优点,并通过后续工艺对其组织进行调控,则是制备高强高导铜合金的一条新路径。实验通过真空感应熔炼的方法制备了复杂多组元Cu-0.746Cr-0.217Zr-0.605Ni-0.109Si-0.177Co-0.085Zn(质量分数)合金,对其进行了不同工艺条件的固溶处理,并研究了不同固溶工艺条件下,合金时效过程中电导率及硬度的演化规律。结果表明:合金经1010℃×1.5 h固溶处理后,时效过程在500℃×3 h时,可获得较优异的综合性能,此时合金的硬度为HV 142.83,电导率为60.00%IACS。此外,根据Avrami经验方程描述了合金的时效析出过程,发现不同固溶工艺的合金在时效过程中,析出速率均随时效温度的提高而提高。

Hydrothermal Synthesis, Crystal Structure and Properties of One Binuclear Nickel(Ⅱ) Complex with 3-(2-Pyridiyl)-1H-1,2,4-triazole

A new binuclear nickel（Ⅱ） complex [Ni_2（C_7 N_4 H_5）_3（C_9 H_9 O_2）]n has been hydrothermally synthesized with nickel sulfate, 3-（pyridin-2-yl）-1H-1,2,4-triazole and 3,5-dimethylbenzoic acid（3,5-DMBA）. It crystallizes in the triclinic space group P1 with a = 11.5769（7）, b = 12.3115（7）, c = 12.6431（7） A, α = 81.4860（10）o, β = 64.2830（10）o, γ = 63.7130（10）o, V = 1453.45（15） A^3, D_c = 1.604 g/cm^3, Z = 2, F（000） = 720, the final GOOF = 1.048, R = 0.0285 and wR = 0.0628. The crystal structure shows that the whole molecule consists of two nickel ions bridged by three μ_2-η~1：η~0-3-（pyridin-2-yl）-1,2,4-triazole anions. The coordination environment of Ni（Ⅱ） ion is NiO_2 N_4 and NiN_5, giving a distorted octahedral geometry and square pyramidal geometry respectively. The luminescence and thermal properties of the complex were investigated.