Synthesis and Characterization of Nickel(II) and Copper(II) Complexes with Schiff Base (1R,2R)-(-)-Diaminocyclohexane-N,N'-bis(3-tert-butyl-5-(4'-benzoic acid)-salicylidene)

Two homochiral metallosalen complexes, Ni（salen） （salen = （1R,2R）-（-）-diamino- cyclohexane-N,N′-bis（3-tert-butyl-5-（4′-benzoic acid）-salicylidene） 1 and Cu（salen） 2, have been synthesized and characterized by IR, microanalysis, TGA, powder and single-crystal X-ray crystallography. Both 1 and 2 crystallize in orthorhombic space group P21212 with Z = 4. For 1, a = 12.082（2）, b = 15.447（3）, c = 18.784（4）A^°, V= 3505.7（12）A^°3, Mr = 731.50, Dc = 1.386 g/cm^3, μ = 0.606 mm^-1, F（000） = 1544, the final GOOF = 1.043, R = 0.0496 and wR = 0.1248 for 4791 observed reflections with I 〉 2σ（I）. For 2, a = 12.181（2）, b = 15.501（3）, c = 18.877（4） A^°, V = 3564.3（12）A^°3, Mr = 736.33, Dc = 1.372 g/cm^3, μ = 0.665 mm^-1, F（000） = 1548, the final GOOF = 1.062, R = 0.0575 and wR = 0.1508 for 4562 observed reflections with I 〉 2σ（I）. The crystal structures of 1 and 2 are isostructural with very similar supramolecular structures. An infinite two-dimensional network is generated by hydrogen bonding interactions and intermolecular π…π interactions.

DNA Cleavage of the Copper(II) Complexes with a Polyamine Ditopic Ligand

A new binuclear complex [Cu2L(OH)](ClO4)3·2H2O has been synthesized and characterized, where L=2,6-bis{[bis-(2-aminoethyl)amino]methyl}-benzene. In the presence of 0.5 mmol/L complex at pH 8.10 and 37°C, the complex can efficiently cleavage pBR322 DNA with a rate constant kobs of 1.35×10-4 s-1. The cleavage occurred by a non-oxidative mechanism showing activity to be dependent on pH.

Copper（II） Complexes Based on 4＇-R-Terpyridine： Synthesis, Structures, and Photocatalytic Properties

Complexes Cu（II）（4＇-R-terpyridine）2（C104）2[R=2-thienyl（1）, 2-（5-bromothienyl）（2）, 2-（5-methyl- thienyl）（3） and 2-（5-methoxythienyl）（4）] were synthesized, and their structures were determined by single-crystal X-ray diffraction analyses and were further characterized by high resolution mass spectrometry, infrared spectrosco- py（m）, as well as elemental analysis. Single crystal X-ray diffraction analysis shows that Cu（II） ions in the complexes are both six-coordinated with N6 coordination sphere, displaying distorted octahedral geometries. In addition, the UV-Vis absorption spectra show that the four complexes all exhibit absorption components in both UV and visible light regions. Thus, the photocatalytic activities of the four complexes in the degradation of organic dyes were investigated.

Syntheses and Crystal Structures of Two Copper(II) Complexes Derived from Bidentate Schiff Bases

Two new Cu（Ⅱ） complexes have been synthesized with two different bidentate N2O2 donor Schiffbase ligands HL1 （2-（（E）-（4-chlorophenylimino）methyl）-6-bromo-4-chlorophenol） and HL2 （2-（（E）-（2-chlorophenylimino）methyl）-6-bromo-4-chlorophenol）, respectively. Both complexes 1 and 2 have been characterized by elemental analysis and single-crystal X-ray diffraction studies. Structural studies reveal that in both complexes the metal centers are four-coordinated with N202 donor set of Schiff base ligands. Complex 1 belongs to the tetragonal system, space group P4（3）2（1）2 with a = 10.2379（2）, b = 10.2379（2）, c = 24.9623（90） A, V = 2616.41（12） A^3, Z = 4, Dc = 1.908 g/cm^3,μ（MoKa） = 4.3327 mm^-1, F（000） = 1468, S = 0.999, the final R = 0.0345 and wR = 0.0835 for 3506 unique reflections （Rint= 0.0428） with 3249 observed ones （I 〉 2σ（I））. Complex 2 is of monoclinic system, space group P21/c with a = 11.064（3）, b = 9.437（2）, c = 13.277（4） A, fl = 108.997（3）°, V = 1310.8（6） A^3, Z = 2, Dc= 1.904 g/cm^3,μ（MoKa） = 4.319 mm^-1, F（000） = 734, S = 0.997, the final R = 0.0282 and wR = 0.0619 for 3491 unique reflections （Rint = 0.0428） with 2777 observed ones （I 〉 20（I））. The units of the complex are linked via weak interactions, such as C-H…Br hydrogen bonds together with Cl…C1 and Cu…Cl interactions, leading to the formation of one-dimensional chain and two-dimensional network and stabilizing the crystal structure.

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.

Theoretical Studies on the Spin Exchange Interaction in Copper(II) Complexes Coordinated with Nitronyl Nitroxide

Nitronyl nitroxide radical 1, NIT (4, 4, 5, 5-tetramethyl-4, 5-dihydro-1H-imidazolyl-1- oxyl-3-oxide) and copper(II) chloride complexes with nitronyl nitroxide 2, [Cu(NITPh)2Cl2] (NITPh = 2-phenyl-4, 4, 5, 5-tetramethyl-imidazoline-1-oxyl-3-oxide) were studied with density functional theory (DFT). The magnetic orbital analysis reveals that the antiferromagnetic coupling for complex 2 is due to the antibonding s*-orbital overlap between 22x-yd(Cu) and p* (NO) orbitals. Also, spin population and atomic charge distribution analysis suggest that for AFS of complex 2 the antiferromagnetic coupling between the radical ligands and the copper(II) ion originates from the spin delocalization induced by the a electron transfer from p*(NO) to 22x-yd(Cu) orbital.

Preparation of Platinum(II) Complexes with 1-β-D-Ribofuranosyl-1,2,4-triazole-3-carboxamide and its Deoxy-analogue

The platinum (II) complexes of the [Pt (N4,N7-Ribavirin) (DMSO) Cl], [Pt (N4,N7-De-oxyribavirin) (DMSO) Cl] were obtained by the reactions of cis-[Pt (DMSO)2 Cl2] and K[Pt (DMSO) Cl3] with 1-??-D-ribofuranosyl-1,2,4-triazole-3-carboxamide (Ribavirin) and its deoxy-analogue (deoxyribavirin). The preparation of 1-(2'-deoxy-?-D-ribofuranosyl) -1,2,4-triazole-3-carboxamide was also performed through a four-step procedure, protection of 3', 5'-dihydroxyl group of Ribavirin with 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane (TPDS-Cl), phenoxythio-carbonylation of the 2'-hydroxyl group of 3', 5'-O-TPDS-Ribavirin with phenoxythiocarbonyl-chloride (PTC-Cl), reduction of 2′-O-phenoxythiocarbonyl ester of 3', 5'-O-TPDS-Ribavirin with tri-n-butyltin hydride and AIBN, deprotection of 3', 5'-O-TPDS-Ribavirin with tetrabutylammon-ium fluoride in THF.

Synthesis, Structure and Fluorescence of a Copper(II) Complex [Cu_2(bipy)_2(Hpht)_2Cl](Hpht)(bipy=2,2'-Bipyridine,H_2pht=o-Phthalic Acid)

The title complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2?-bipyridine, H2pht = o-phthalic acid) has been synthesized in the NaOH aqueous solution of CuCl2, Gd(NO3)3, bipy and H2pht, and its crystal structure was determined by single-crystal X-ray diffraction method. It crys- tallizes in triclinic, space group P1, C44H31ClCu2N4O12, Mr = 970.26, a = 8.175(2), b = 16.254(4), c = 16.946(4) ?, α = 62.966(6), β = 84.833(8), γ = 84.348(8)°, V = 1993.4(8) ?3, Z = 2, Dc = 1.616 g/cm3, F(000) = 988 and μ = 1.207 mm-1. The final R = 0.0429 and wR = 0.0843 for 5682 observed reflections with I > 2σ(I). Each copper(II) atom displays a distorted square-pyramidal geometry with two nitrogen atoms of one chelate 2,2?-bipy molecule, two oxygen atoms from two different bridging carboxylate groups of Hpht- and one bridging chloride atom occupying the apical position. The two copper(II) atoms are connected by a μ2-Cl atom and two bridging Hpht- ligands in a syn-syn coordination mode to form an isolated dinuclear unit. The molecular structure is extended to a one-dimensional wavy chain through hydrogen bonds. The title complex exhibits blue fluorescent emission at 443 nm (λex = 372 nm) in the solid state at room temperature.

Dioxygen Affinity and Catalytic Performance of Bis-(furaldehyde) Schiff Bases Co(II) Complexes in Cyclohexene Oxidation

Oxygenation constants and thermodynamic parameters DeltaH degrees and DeltaS degrees of cobalt (II) complexes with bis-(furaldehyde) Schiff bases (1, 2, 3, 4)were obtained by mearsuring saturated dioxygen uptake of these complexes in pyridine at different temperature. These complexes could activate molecular oxygen and were used as catalysts in cyclohexene oxidation. The influence of ligand structure on the dioxygen affinity and catalytic activity of the complexes were discussed.

Hydrothermal Synthesis and Structure of a Copper(II) Complex, [Cu(4,4'bpy)(H_2O)_3]SO_42H_2O

The title complex [Cu(4,4?bpy)(H2O)3]SO42H2O (Mr = 405.86) was synthesized under hydrothermal conditions and its crystal structure has been determined by X-ray diffraction. It crystallizes in the hexagonal system, space group P61 with a = 11.1870(4), c = 21.578(1) ? V = 2338.6(2) ?, Dc = 1.729 g/cm3, Z = 6, m(MoKa) = 1.583 mm-1 and F(000) = 1254. The final R and wR are 0.0253 and 0.0416 for 1458 observed reflections with I≥2s(I), respectively. It was revealed that the square pyramidal Cu(II) sites are linked through 4,4?bipyridine groups, forming infinite one-dimensional chains, with the sulfate anions and lattice water molecules occupying the inter-chain positions. During the electrostatic interactions, there exist O…O hydrogen bonds and p-p stacking interactions between the parallel aromatic bipy rings in the structure.

Synthesis and Crystal Structure of a New Copper(II) Complex with 4-Cyanobenzoic Acid

A new Cu（Ⅱ） complex [Cu（4-cba）（1,10-phen）（H2O）2]（NO3） （4-Hcba = 4-cyanobenzoic acid） has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characterized by single-crystal X-ray diffraction. Crystallographic data： C20H16CuN4O7, Mr= 487.91, triclinic, space group PI, a = 7.8420（2）, b = 9.1070（2）, c = 15.1140（6） A, a = 76.889（9）, β = 81.332（11）, γ = 74.844（ 11）°, V = 1009.89（5） A^3, Z = 2, Dc = 1.605 g/cm^3, F（000） = 498, μ = 1.134 mm^-1, the final R = 0.0379 and wR = 0.0865 for 2977 observed reflections with 1 〉 2σ（Ⅰ）. The Cu（Ⅱ） atom is coordinated by two terminal water molecules, one chelating 1,10-phen molecule and one monodentate 4-cba ligand to form a slightly distorted square pyramid. The title complex molecules are connected through hydrogen bonds and π-π stacking interactions to generate a 2D layered network. The thermogravimetric analysis of the title complex has also been discussed.

Synthesis, structure, DNA binding and cleavage activity of a new copper(II) complex of bispyridylpyrrolide

A copper-bispyridylpyrrolide complex [Cu(PDPH)Cl](PDPH = 2,5-bis(2′-pyridyl)pyrrole) was synthesized and characterized. The complex crystallizes in the orthorhombic system with space group Pccn, a = 0.9016(3) nm, b = 1.0931(4) nm, c =2.5319(8) nm, and V = 2.4951(15) nm3. The copper center is situated in a square planar geometry. The interaction of the copper(II)complex with calf thymus DNA(CT-DNA) was investigated by electronic absorption, circular dichroism(CD) and fluorescence spectra. It is proposed that the complex binds to CT-DNA through groove binding mode. Nuclease activity of the complex was also studied by gel electrophoresis method. The complex can efficiently cleave supercoiled p BR322 DNA in the presence of ascorbate(H2A) via oxidative pathway. The preliminary mechanism of DNA cleavage by the complex with different inhibiting reagents indicates that the hydroxyl radicals were involved as the active species in the DNA cleavage process.

Hydrothermal Synthesis,Crystal Structure and Electrochemical Properties of the Copper(II) Complex [Cu_4O_4(phen)_4(ClC_6H_4COO)_2(H_2O)_2]·(H_2O)_3

The title complex of copper（Ⅱ） with m-chlorobenzoic acid, 1,10-phenanthroline （phen） and copper perchlorate has been synthesized and characterized in the solvent mixture of water and methanol. Crystal data for this complex： triclinic, space group PI^-, a = 1.06853（12）, b = 1.30740（16）, c = 1.49546（17） nm, α= 101.791（2）,β = 103.413（2）, γ = 105.815（2）°, V= 1.8736（4） nm^3, Mr = 904.67, Dc = 1.604 g/cm^3, Z = 2,/7（000） = 924,μ = 1.34 mm^-1, GOOF = 1.049, the final R = 0.0324 and wR = 0.0797. The structure analysis shows that a chair-like structure [Cu4O4] is defined by three quadrilaterals shaped by four copper and four oxygen atoms, and every copper ion is coordinated by three oxygen atoms from three wate： molecules and two nitrogen atoms from one 1,10-phenanthroline molecule, giving a distorted square-pyramidal coordination geometry. The CV analysis results indicate that the electron transfer in the electrode reaction is quasi-reversible.

Rapid, Catalytic Hydrolysis of DNA by Copper(Ⅱ) Complexes

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Synthesis and Crystal Structure of a Copper(II) Complex with 2,4-Dihydroxybenzylidene Benzoylhydrazone Ligand

A new copper（Ⅱ） complex with formula CuL（py）, where L^2- is the dianion of 2,4-dihydroxybenzylidene benzoylhydrazone, has been synthesized and characterized by IR spectra and single-crystal X-ray diffraction method. The crystal belongs to monoclinic, space group P2 1/c with a=0.9630（4）, b=1.4808（6）, c=1.2320（5） nm, β=104.969（6）°, V=1.6973（Ⅱ） nm^3, Z=4, Dc=1.553 g/cm^3,μ（MoKa）=1.311 mm^-1, F（000）=812, R=0.0694 and wR=0.1727 for 1511 observed reflections （I〉2σ（I））. The crystal structure analysis indicates that the copper（Ⅱ） ion lies in a distorted square-planar environment composed of two oxygen atoms, one nitrogen atom from the tridentate acylhydrazone Schiff base ligand L^2- and one nitrogen atom from the pyridine ligand. Two adjacent molecules are connected via weak Cu…O bonding interactions to form dimers, which are further linked to generate a two-dimensional layer structure via interdimeric hydrogen bonds.

Syntheses, Structures and Photoluminescence of the Cadmium(Ⅱ) and Copper(Ⅱ) Complexes Based on 4'-(4''-Pyridyl)-2,2':6',2''-terpyridine and 1,4-Benzenedicarboxylic Acid Ligands

Two new metal-organic complexes [Cd2（1,4-BDC）（4-pytyp）（H2O）4]·（1,4-BDC）（1） and [Cu2（1,4-BDC）（4-pytyp）2（H2O）2]·（1,4-BDC）·8H2O（2）（4-pytyp = 4＇-（4＇＇-pyridyl）-2,2＇：6＇,2＇＇-terpyridine, 1,4-H2 BDC = 1,4-benzenedicarboxylic acid） have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared analysis and X-ray single-crystal diffraction. The scrutiny of single-crystal structure reveals that complex 1 forms to a 3D supramolecular network linked by π-π stacking interactions and hydrogen bonds. X-ray diffraction analysis reveals that complex 2 exhibits a 3D supramolecular network linked through complicated hydrogen bonds. The thermogravimetric analysis and photoluminescent properties of 1 and 2 are discussed in detail.

Synthesis, Structure and Spectral Characterization of a Discrete Binuclear Copper (II) Complex

A discrete binuclear copper (II) complex containing Cu 2O 2 unit has been synthesized by the reaction of Cu (ClO 4) 2·6H 2O with 2 aminopyridine in the CH 3OH solution and characterized by X ray diffraction study and IR spectroscopy. The crystal is monoclinic, space group: P2 1/n, with unit cell parameters: a=8.2952(2), b=18.4633(3), c=10.5049(2) . β=108.965(1)°, V=1521.56(5) 3, Z=2, C 22 H 30 N 8O 10 Cl 2Cu 2, M r =764.52, D c =1.669 Mg/m 3, F(000)=780, μ (Mo Kα )=8.60, T =293(2)K, final R=0.0623, wR =0.1536 for 2660 observed reflections with I>2.0σ(I ). The centrosymmetric complex Cu 2(CH 3O) 2(C 5H 6N 2) 4(ClO 4) 2 comprises a pair of Cu(II) atoms bridged by two methanoxo and N coordination 2 aminopyridine. The Cu(II)…Cu(II) distance is 3\^002(1).

Synthesis and Characterization of Chiral Mercury(II) and Cadmium(II) Complexes with 3,3'-Bipyridine-5,5',6,6'-tetramethyl-2,2'-dimethoxy-1,1'-biphenyl

Two homochiral mercury （1） and cadmium （2） complexes derived from chiral twisted biphenyl pyridine ligand （3,3＇-bipyridine-5,5＇,6,6＇-tetramethyl-2,2＇-dimethoxy-1,1＇-biphenyl） have been synthesized and characterized by IR, microanalysis, TGA, UV-Vis, powder and single-crystal X-ray crystallography. Both 1 and 2 crystallize in orthorhombic space group P21212 with Z = 2. For 1, a = 14.2038（16）, b = 14.3630（17）, c = 7.0257（8）, V = 1433.3（3）3, Mr = 878.91, Dc = 2.037 g/cm3, μ = 7.549 mm-1, F（000） = 824, the final GOF = 1.017, R = 0.0296 and wR = 0.0645 for 2925 observed reflections with I 2σ（I）. For 2, a = 14.212（3）, b = 14.392（3）, c = 7.0498（14）, V = 1442.0（5）3, Mr = 790.72, Dc = 1.821 g/cm3, μ = 2.924 mm–1, F（000） = 760, the final GOF = 1.075, R = 0.0340 and wR = 0.0834 for 3144 observed reflections with I 2σ（I）. The crystal structures of 1 and 2 are isostructural and each adopts a two-dimensional supramolecular network which contains the C–H···π interactions.

Synthesis,Structure and Magnetic Properties of Novel Carboxylato-bridged Pentanuclear Copper(Ⅱ)-Lanthanoid(Ⅲ)Complexes

Six novel pentanuclear complexes [Cu 3Ln 2(ClCH 2CO 2) 12 (H 2O) 8]·2H 2O (Ln=La, Pr, Sm, Gd, Dy, or Er) were synthesized by the reaction of chloroacetic acid with Cu and Ln ions in aqueous solutions. The X ray crystallography established the structure of the Gd complex, which contains a pair of quadruply acetato bridged CuGd dinuclear subunits, and each of them is linked to the central Cu atom by a single acetato bridge. The coordination sphere of each Gd atom is completed by three aqua ligands [Gd-O=0.242 8(5)-0.244 4(4) nm] to form an 8 coordinated distorted square antiprism. The central Cu atom is coordinated by two oxygen atoms from the two bridging acetato groups and two oxygen atoms from the two monodentate acetato groups in a slightly distorted square planar fashion, while each terminal Cu atom is coordinated by the four acetato oxygen atoms at the basal plane and an aqua ligand at the apical position to form a square pyramid. The variable temperature (4 320 K) magnetic susceptibility data of the Gd complex were measured, and fitted to the Curie Weiss law with C =16.38 K cm 3·mol -1 and θ =-1.55 K, indicating very weak antiferromagnetic interaction.