Synthesis, Spectroscopic and Electrochemical Investigations of Two vic-Dioximes and Their Mononuclear Ni（Ⅱ）, Cu（Ⅱ） and Co（Ⅱ） Metal Complexes Containing Morpholine Group

Two vic-dioxime ligands （LxH2） containing morpholine group have been synthesized from 4-[2-（dimethylaminoethyl）] morpholine with anti-phenylchloroglyoxime or anti-monochloroglyoxime in absolute THF at -15 ℃. Reaction of two vic-dioxime ligands with MCl2·nH2O （M： Ni, Cu or Co and n=2 or 6） salts in 1 ： 2 molar ratio afforded metal complexes of type [M（LxH）2] or [M（LxH）2·2H2O]. All of metal complexes are non-electrolytes as shown by their molar conductivities （Am） in DMF （dimethyl formamide） at 10^-3 mol·L^-1. Structures of the ligands and metal complexes have been solved by elemental analyses, FT-IR, UV-Vis, ^1H NMR and ^13C NMR, magnetic susceptibility measurements, molar conductivity measurements. Furthermore, redox properties of the metal complexes were investigated by cyclic voltammetry.     

Crystal Structures and Theoretical Calculation of Zn（Ⅱ） and Cu（Ⅱ） Supramolecular Complexes Based on Macrocyclic Triamine Ligand 1,4,7-Triazacyclodecane （tacd）

Two supramolecular complexes [Zn（tacd）2]（C6H8O4）·6H2O（1） and [Cu（tacd）2]Cl2·4H2O（2） were synthesized and characterized by elemental analysis, IR spectra, TGA and single-crystal X-ray diffraction analysis. The crystal structure showed that the metal ions in complexes 1 and 2 had similar coordination circumstance. But for the complex 2, it formed a novel two-dimensional supramolecular network with 12-membered rings and four-membered rings via hydrogen bond interaction. The thermal gravimetric analyses indicated that the two complexes had similar steps of weight-loss. On the basis of experiment, the two complexes were calculated by DFT-B3LYP/6-31G（d） in Gaussian 03. The results of calculation are in good agreement with the experiment.     

Synthesis,Characterization and SOD Activities of IP-copper（Ⅱ）-L-amino Acid Complexes

Four new ternary complexes： [Cu（IP）（L-Val）（H2O）]ClO4·1.5H2O（1）, [Cu（IP）（L-Leu）（H2O）]ClO4（2）, [Cu（IP）（L-Tyr）（H2O）]ClO4·H2O（3） and [Cu（IP）（L-Trp）（H2O）]ClO4·1.5H2O（4） have been synthesized and character/zed by elementa/analysis, molar conductivity, infrared absorption spectroscopy, electronic absorption spectroscopy and cyclic voltammetry, where IP=imidazo[4,5-f][1,10] phenanthroline, L-Val=L-valinate, L-Leu=L-leucinate, L-Tyr=L-tyrosinate and L-Trp=L-tryptophanate. Complex 3 was structurally characterized by X-ray diffraction method, which crystallizes in orthorhornbic space group P21212 in a unit cell of dimensions a=3.0567（4） nm, b=0.74079（9） nm, c= 1.06198（13） nm, V=2.4047（5） nm^3, Z=4,μ=0.1084 cm^-1. The SOD-like activities of catalytic disrnutation of superoxide anions （O2^-· ） by the complexes were determined by means of modified nitroblue tetrazolium （NBT） photoreduction. The IC50 values of complexes 1, 2, 3 and 4 are 0.072, 0.147, 0.429 and 0.264 μmol·L^-1, respectively     

Syntheses and Crystal Structures of Three Cadmium（II） Coordination Complexes Based on Flexible 1,2-Bis（imidazol-1~ˊ-yl）ethane

Three Cd（II） coordination complexes,{[Cd（bime）3]（NO3）2·（H2O）3}n（1）,[Cd（bime）Br2]n（2） and [（H2bime）（CdBr4）（H2O）]n（3）（bime = 1,2-bis（imidazol-1-yl）ethane）,have been prepared and characterized.Single-crystal X-ray diffraction analysis reveals that 1~3 crystallize in the trigonal space group P-3,monoclinic space group C2/c and triclinic space group P1,respectively.In 1,bime bridges six-coordinated Cd（II） to generate a two-fold interpenetrating 3D coordination polymer,in which NO3- is not involved in coordination,but serves as a void filler to balance the charge of the 3D framework.The six NO3- and six uncoordinated water molecules form an unprecedented 24-membered macrocycle through hydrogen bonding interaction.In 2,bime in an anti-conformation links the CdBr2 units into a zigzag chain.In 3,bime does not take part in coordination,but is protonated to act as a counter cation of [CdBr4 ]2-.The hydrogen bonds between H2bime and [CdBr4]2- result in the formation of a supramolecular chain.     

Four New Cu（Ⅱ） Complexes with Benzotriazole-based Ligands： Syntheses,Crystal Structures and Theoretical Investigations

Four new Cu（Ⅱ） complexes with two benzotriazole-based ligands, [Cu2（L^1）2（NO3）2]· 2H2O （1）, [Cu2（L^1）2]·2ClO4·2H2O （2）, [Cu2（HL^2）2（NO3）4]·2CH3COCH3 （3） and [Cu（HL^2）2（Cl）]·Cl·2CH2Cl2 （4）, where HL^1 = 1,3-bis（benzotriazol-2-yl）-2-propanol and HL^2 = 1,3-bis（benzotriazol-1-yl）-2-propanol, were synthesized and structurally characterized by elemental analyses, IR and single-crystal X-ray diffraction analyses. It is revealed that complexes 1～3 have dinuclear structures, while 4 possesses a one-dimensional （1-D） chain structure, which extends in two orthogonal orientations. In 1～4, the coordination numbers of Cu（Ⅱ） centers range from four to six, which may be attributed to the different geometries and coordination abilities of the ligands and anions. The L^1 ligand in complexes 1 and 2 adopts a tridentate di-chelating coordination mode, whereas ligand HL^2 in complexes 3 and 4 has a bidentate bridging coordination mode. The different coordination modes of these two ligands may be explained by the different charges of nitrogen donor atoms in the benzotriazole ring, which has been investigated by density functional theory （DFT） calculations.     

咪唑-金属配合物的合成、性质及其与DNA的作用机理

Three hexakis（imidazole）metallo complexes of Co, Cd and Ni were synthesized and spectroscopically characterized. The crystal and molecular structures have been determined by X-ray crystallography analysis. The metal ions have an octahedral geometry with the MN6 chromophore. The electrochemical experimental results indicate that both [Co（Im）6]C12·2HCl·2H2O （1） and [Ni（Im）6]C12·4H2O （3） [Im=imidazole] could interact with DNA mainly by intercalation.     

Electron Effect of p-Substituent on Iron（Ⅱ） and Cobalt（Ⅱ） Pyridinebisimine Catalyst for Ethylene Polymerization

A series of 2,6-bis（imino）pyridyl iron and cobalt complexes bearing p-substituent [2,6-（ArN=CMe）2C5H3N]- MCl2 （Ar=2,6-Me2C6H3, 2,4,6-Me3C6H2, 2,6-Me2-4-BrC6H2, 2,6-Me2-4-ClC6H2, 2,4-Me2-6-BrC6H2, 2,4-Me2-6- ClC6H2, while M=Fe, Co） have been synthesized and investigated as catalysts for ethylene polymerization in the presence of modified methylaluminoxane as a cocatalyst. The electron effect and positions of the substituent of pyridinebisimine ligands were observed to affect considerably catalyst activity and polymer property.     

Syntheses and Structures of Two New Cobalt Supramolecular Complexes, [Co（4,4＇-bipy）2（H2O）4]·[Co2（4,4＇-bipy）3（H2O）8]·2TST·2（4,4＇-bipy）·4H2O and [Co（4,4＇-bipy）2（H2O）4]DSNT·4,4＇-bipy

Two new cobalt（II） supramolecular complexes [Co（4,4＇-bipy）2（H2O）4]·[Co2（4,4＇-bipy）3（H2O）8]·2TST·2（4,4＇-bipy）·4H2O 1 and [Co（4,4＇-bipy）2（H2O）4]DSNT·4,4＇-bipy 2 based upon the assembly of Co（II）, 4,4＇-bipyridine （4,4＇-bipy） and two new multifunctional organic ligands, 2,4,6-tris（4-sulfophenyl- amino）-1,3,5-triazine （H3TST） and 2,4-bis（p-sulfanilato）-6-diethylamino-1,3,5-triazine （H2DSNT）, have been prepared by hydrothermal method and characterized by elemental analysis, IR spectrum, and single-crystal X-ray diffraction. The crystal structure of 1 is of monoclinic, space group P21/n with a = 13.599（4）, b = 18.988（6）, c = 22.995（7） A, β = 90.273（6）°, V = 5938（3）A^3, Z = 4, C56H59Co1.5N13O17S3, Mr = 1370.74, Dc = 1.533 g/cm^3, μ = 0.613 mm^-1, F（000） = 2842, GOOF = 1.018, the final R = 0.0796 and wR = 0.1498 for 9019 observed reflections with I 〉 2σ（I）. The crystal structure of 2 belongs to the monoclinic system, space group C2/c with a = 18.864（6）, b = 14.283（5）, c = 20.246（7）A, β = 107.799（6）°, V = 5194（3）A^3, Z = 4, C49H52CoN12O10S2, Mr = 1092.08, Dc = 1.397 g/cm^3, μ = 0.480 mm^-1, F（000） = 2276, GOOF = 1.059, the final R = 0.0665 and wR = 0.1900 for 4887 observed reflections with I 〉 2σ（I）. The results of X-ray crystal structure analysis revealed that complexes 1 and 2 exhibit layered supramolecular frameworks stabilized by electrostatic interactions, π-π interactions and hydrogen bonds.     

Synthesis and Crystal Structure ofa Bipy Bridged Binuclear Cu^Ⅱ Complex Containing Aminomethanesulfonic Acid [Cu2（Sams）2（Bipy）（H2O）2]·（H2O）

The title complex [Cu2（Sams）2（H2O）2（bipy）]·（H2O） 1 （H2Sams = N-（2-hydroxybenzy） aminomethanesulfonic acid, bipy = 4,4′-bipyridine） has been synthesized by the reaction of Cu- （CH3COO）2·H2O, nESams and 4,4′-bipyridine in aqueous methanol. It was characterized by IR, elemental analysis, thermogravimetric analysis （TGA） and X-ray diffraction analysis. Complex 1 crystallizes in monoclinic, space group P21/n with a= 10.9533（17）, b = 8.3408（13）, c = 16.714（3） A^°, β = 101.295（4）°, V = 1494.3（4） A^°3 and Z = 2. The asymmetric unit is comprised of a tridentate Schiff base Sams^2- anionic ligand, a 4,4′-bipyddine and two coordinated water molecules, thus forming a binuclear copper（Ⅱ） complex. The coordination environment at Cu^Ⅱ center is described as a slightly distorted square pyramidal geometry. Via intermolecular hydrogen bonds C（10）-H（10）…O（3） and C（13）- H（13）…O（3）, an infinite supramolecular chain is yielded. A number of intermolecular hydrogen bonds greatly contribute to the stabilization of the solid-state structure for 1.     

Synthesis,Characterization and Crystal Structure Determination of a Thiocyanato Bridged One-dimensional Polymeric Complex of Cadmium（Ⅱ）

A new one-dimensional polymeric complex [Cd（SCN）2（H2O）]L （L = N,N′-bis（furan- 2-ylmethylene）hydrazine） has been synthesized and characterized by IR, UV spectra, TG-DTA technique and single-crystal X-ray diffraction analysis. It crystallizes in triclinic, pace group P1^- with a = 5.9268（8）, b = 10.8678（15）, c = 13.3671（19） A, α = 109.295（2）, β = 95.092（2）, γ = 97.8580（10）°, V = 796.70（19）A^3, Z = 2, C12H10CdN4O3S2, Mr = 434.76, μ = 1.648 mm^-1, Dc = 1.812 g/cm^3, F（000） = 428, R = 0.0308 and wR = 0.0769. The crystal structure reveals that the structure of [Cd（SCN）2（H2O）]n features di-μ-1,3-thiocyante bridges and 1D chains. The octahedrally coordinated Cd atom is surrounded by one oxygen atom from water molecule, three S atoms and two N atoms from five di-μ-1,3 thiocyanato bridges. The Cd atoms are connected by two di-μ-1,3 thiocyanato bridges with the Cd（1）…Cd（1A） separation of 4.239（1） A and Cd（1）...Cd（1B） of 5.852（1）/~. In addition, the one-dimensional straight chain structure is further connected by multiform intermolecular N-H…O hydrogen bonds and π-π interactions to form a three-dimensional supramolecular structure.     

Crystal Structure, Thermal Stability and Luminescence of Coordination Polymer [Cd（BBP）（p-PDOA）]n

Hydrothermal reaction of Cd（NO3）2·4H2O with bbp and p-PDOAH2 at 140 ℃ yielded a novel 1D cadmium（Ⅱ） coordination polymer, [Cd（bbp）（p-PDOA）]n （bbp=2,6-bis（benzimidazol-2-yl）pyridine, p-PDOA=p-phenylenedioxydiacetate dianion）, in which CdN3O4 pentagonal bipyramids were linked by p-PDOA ligands in a bis-bidentate mode to construct a zigzag chain with the adjacent Cd…Cd distance of 1.14（1） nm, There exists a 2D supramolecular network linked by π-π stacking with a face-to-face distance of 0.35（1） nm between the 2,6-bis（benzimidazol-2-yl） pyridine ligands and hydrogen-bonding interactions （0.27（4） nm）. A 3D supramolecular network was further constructed by these non-covalent interactions between the zippers. The TG/DTG showed that its chain skeleton was thermally stable up to 389 ℃ and the blue fluorescent emission of the complex was determined at 428 nm in a solid state with its long decay lifetime of 7.24 ns.     

Synthesis and Crystal Structure of Di-μ1,1-azido-bis（（azido）[N-ethyl-N＇-（1-pyridin-2-ylmethylidene）ethane-1,2-diamino]cadmium（Ⅱ））

The dinuclear Schiff base cadmium（Ⅱ） complex [Cd2（C10H15N3）2（N3）2 （μ1,1-N3）2] was prepared and characterized by elemental analysis, IR spectrum, and single-crystal X-ray dif- fraction. The crystal belongs to the monoclinic system, space group P21/n with a = 10.819（2）, b = 11.058（2）, c = 12.766（3）A, β = 102.456（2）°, V = 1491.3（7）A^3, Z = 2, Dc = 1.665 g/cm^3, Mr = 747.42, λ（MoKα） = 0.71073 （A）, μ = 1.470 mm^-1, F（000） = 744, R = 0.0307 and wR = 0.0584. A total of 3420 unique reflections were collected, of which 2575 with Ⅰ 〉 2σ（Ⅰ） were observed. There is a crystallographic inversion centre at the midpoint of the two metal atoms in the complex. Each CdⅡ atom in the complex is in a distorted octahedral coordination. The molecules in the crystal are linked through the intermolecular hydrogen bonds of N-H…N and C-H…N, forming a three- dimensional network.     

Synthesis, Crystal Structure, UV-vis and EPR Studies of（ NH3CH2CH2NH2 ） 2.5 [ Mo0.5^（V）W0.5^（VI）O2 （ OC6H4O ） 2]

Cis-dioxo-metal complex ( NH3CH2CH2NH2 ) 2.5 [ Mo0.5^(V)W0.5^(VI)O2 ( OC6H4O ) 2] 1 was obtained by the reaction of tetra-butyl ammonium hexamolybdotungstate with 1, 2-dihydroxybenzene in the mixed solvent of CH3OH, CH3CN and ethylenediamine,and characterized by X-ray diffraction, UV-vis and EPR analysis. Compared with its analogous complexes (NH3CH2CH2NH2)3[Mo^(V)O2(OC6H40)2] 2 and (NH3CH2CH2NH2)2[W^(VI)O2(OC6H4O)2] 3, the results show that tungsten(VI) is less active in redox than molybdenum (VI) and that the change of the valence induced by substitution of W(VI) for Mo(V) in EMO2(OC6H40)2]n- does not influence the coordination geometry of the complex anion in which the metal center exhibits distorted octahedral coordination with cis-dioxo catechol. The responses to EPR of complexes 1 and 2 are active but complex 3 is silent,and the UV-vis spectra exhibited by the three complexes are obvious different because of the different electronic configuration between the central Mo(V) and W(VI) ions in the complexes.It is noteworthy that complexes 1 and 2 have the similar EPR signal to flavoenzyme, suggesting that the three complexes have the same coordination geometry feature with the co-factor of flavoenzyme.     

2D Naphthalenedisulfonate-cadmiun coordination polymer with 2,4,5-tri（4-pyridyl）-imidazole as a co-ligand： Structure and catalytic property

A new 2D coordination polymer, [Cd（tpim）（1,5-nds）]n （1）, was constructed from 1,5-naphthalenedi- sulfonate （1,5-nds）. 2.4,5-tri（4-pyridyl）-imidazole （tpim） and Cd（CH3COO）2.2H2O, which can be subsequently used to promote the epoxide ring-opening reaction of epoxides and amines with remarkable catalytic activity. In addition, the thermal and luminescent properties of I in the solid state were also investigated.     

Syntheses,Crystal Structures and Properties of Co（Ⅱ） and Cu（Ⅱ） Complexes with 5-Nitro-1,2,3-benzenetricarboxylic Acid

Two new coordination polymers,{[Co(O2N-Hbtb)(phen)(H2O)3]·2H2O}n 1 and {[Cu3(O2N-btb)2(bipy)2(H2O)4]·4H2O}n 2(O2N-H3btb=5-nitro-1,2,3-benzenetricarboxylic acid,phen=1,10-phenanthroline,bipy=2,2'-bipyridine),were prepared through hydrothermal reactions of Co(Ⅱ) or Cu(Ⅱ) salt with O2N-H3btb in the presence of different auxiliary N-donor ligands.Their crystal structures were determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis and IR spectroscopy.In the two complexes,O2N-H3btb ligand acts as monodentate and bis-monodentate modes,respectively.Complex 1 displays a two-dimensional layered structure through the inter-and intramolecular hydrogen bonding interactions while complex 2 has an O2N-btb bridged one-dimensional chain which is extended into a three-dimensional network by hydrogen bonding interactions.The magnetic properties of complex 2 are investigated over the temperature range of 2～300 K and ferromagnetic interactions are observed.     

Syntheses and Structural Characterization of Dimethyltin Complexs of N-（3-Methoxysalicylidene）-α-amino Acid

Three new dimethyltin complexes of N-(3-methoxysalicylidene)-α-amino acid,(CH3)2Sn(3-CH3O-2-OC6H3CH=NCHRCOO)(R = H,1;CH3,2;(CH3)2CH,3),have been synthe-sized by treating dimethyltin dichloride with the potassium salt of the ligand and characterized by elemental analysis,IR and 1H NMR spectra.The crystal structure of [(CH3)2Sn(3-CH3O-2-OC6H3CH=NCH2COO)(CH3OH)]2 H2O(1a),formed from methanol solution of 1,has been deter-mined.The crystal belongs to the monoclinic system,space group C/2c with a = 20.636(3),b = 7.8854(9),c = 20.668(2) ,β= 113.265(2)°,V = 3089.7(6) 3,Z = 4,Dc = 1.707 g/cm3,= 1.675 mm-1,F(000) = 1592,R = 0.0301 and wR = 0.0841.In complex 1a,the tin atom is six-coordinate and possesses a distorted [SnC2NO3] octahedral geometry with the two methyl groups occupying the trans positions.The weak Sn O interactions and intermolecular hydrogen bonds connected the molecules into an infinite chain.     

Synthesis,Crystal Structure and Electrochemistry of Two Complexes （YLn）3＋[PW12O40]3-（L=Me2SO,Me2NCHO）

The reaction of α-H3[PW12O40] with Y（NO3）3 in the presence of DMF or DMSO leads to two complexes with the formulae {Y（DMSO）7}·PW12O40（1） and {[Y（DMF）7]2PW12O40}·PW12O40（2）. The crystal structures indicate that complex 1 consists of discrete [YLn]3＋ cations and α-Keggin heteropolyanions [PW12O40]3-, whereas, in complex 2, donor-acceptor interaction results in a cation-anion-cation triplet. In addition, the electrochemical behavior of the two complexes indicates the usual successive reduction processes of the W atoms in the anions.     

Characterization, Crystal Structure and Initial DNA Binding Interaction of Two Cu（Ⅱ） Complexes with 4,5-Diazafluoren-9-one

Two new complexes [Cu（dafo）2（en）]（ClO4）2·2H2O （en=NH2CH2CH2NH2） 1 and [Cu（dafo）2（dap）]（ClO4）2·2H2O [dap=NH2CH2CH（CH3）NH2] 2 （dafo=4,5-diazafluoren-9-one） have been synthesized and characterized by elemental analysis, IR and UV spectra. Meanwhile, the complex 1 has been characterized by single crystal X-ray diffraction analysis. The initial DNA binding interactions of the complexes 1 and 2 have been investigated by UV spectra, emission spectra and cyclic voltammogram. Concluding the results of three methods used to measure the interaction of complexes 1 and 2 with DNA, the action mode of the two complexes with DNA is intercalation, and character of ligands and steric effect may affect the interaction of the complexes with DNA.     

Synthesis and Reaction of [MnRe（CO）6（μ—SH）（μ—SC（H）PPr^i3）（PPh3）]

The synthesis,the crystal structure and the reaction of the hetero-binuclear complex[MnRe(CO)6(μ-SH）（μ-SC(H)PPr^i3)(PPh3)] are reported.The results of single crystal X-ray structure analysis showed that the fragments Mn(CO)3 and Re(CO)3 were bridged by SH and SC(H)PPr^i3.The title complexes can react with Bu^nLi and RX forming complexes MnRe(CO)6(μ-SR）（μ-SC(H)PPr^i3)(PPh3)](R=Me,CH2CH=CH2,SnBu3^n).     

Cyano-bridged Ln^3＋-Cr^3＋ Binuclear Complexes [Ln（L）x（H2O）y^- Cr（CN）6]·mL·nH2O （Ln=La-Nd,x=5, y=2, m=1 or 2, n=2 or 2.5; Ln-Sm-Dy,Er, x=4, y=3, m=0, n=1.5 or 2.0; L= 2-pyrrolidinone）： Structure,Magnetism and Spin Density Map

In order to shed light upon the nature and mechanism of 4f-3d magnetic exchange interactions, a series of binuclear complexes of lanthanide（3＋） and chromium（3＋） with the general formula [Ln（L）5（H2O）2Cr（CN）6]·mL· nH2O （Ln=La （1）, Ce （2）, Pr （3）, Nd （4）; x=5, y=2, m=1 or 2, n=2 or 2.5; L=2-pyrrolidinone） and [Ln（L）4（H2O）3Cr（CN）6] ·nH2O （Ln=Sm （5）, Eu （6）, Gd （7）, Tb （8）, Dy （9）, Er （10）; x=4, y=3, m=0, n= 1.5 or 2.0; L=2-pyrrolidinone） were prepared and the X-ray crystal structures of complexes 2, 6 and 7 were determined. All the compounds consist of a Ln-CN-Cr unit, in which Ln^3＋ in a square antiprism environment is bridged to an octahedral coordinated Cr^3＋ ion through a cyano group. The magnetic properties of the complexes 3 and 6-10 show an overall antiferromagnetic behavior. The fitting to the experimental magnetic susceptibilities of 7 give g= 1.98, J=0.40 cm^-1, zJ＇= -0.21 cm^-1 on the basis of a binuclear spin system （Scd=7/2, Scr=3/2）, revealing an intra-molecular Gd^3＋-Cr^3＋ ferromagnetic interaction and an inter-molecular antiferromagnetic interaction. For 7 the calculation of quantum chemical density functional theory （DFT）, combined with the broken symmetry approach, showed that the calculated spin coupling constant was 20.3 cm^-1, supporting the observation of weak ferromagnetic intra-molecular interaction in 7. The spin density distributions of 7 in both the high spin ground state and the broken symmetry state were obtained, and the spin coupling mechanism between Gd^3＋ and Cr^3＋ was discussed.