Crystal Structure and Third-order Nonlinear Optical Property Studies on Copper(Ⅱ) Complex Containing NS Donor Ligand

Recently,thestudyofrelationshipsbetweenstructureandpropertyforseriesofcompoundhavingenhancedopticalnonlinearityhasincreaseourunderstandingofwhatmolecularleveIdesigncriteriaareimPortantformaximizingthesecondandthethird-ordernonlinearity'.lngeneral,thesestudieshavefocusedonmanipulationoftheeffectiveconjugationlengthforavarietyofn-electronbackbones,mostlyrelatedto.-PvariousorganiccomPoundscontainingdonorandacceptorgroups'.InthispaPer,wewillstudytheinteractionamongdonor-metal-donorinx-conjugation…     

Crystal Structure and Properties of a Copper(Ⅱ) Complex Containing p-Toluenesulfonate and Imidazole Ligands

A novel supramolecular mixed ligand complex of formula [Cu(PTS)2(Him)2(H2O)2] (C20H26CuN4O8S2,PTS=p-toluenesulfonate,Him=imidazole) has been synthesized in aqueous solution and characterized by elemental analysis,IR and single-crystal X-ray diffraction.The compound crystallizes in the monoclinic system,space group P21/n,Z=2,a=5.650(2),b=14.671(3),c=14.638(3),β=100.10(3)°,V=1194.60(4)3,Dc=1.607 g/cm3,μ(MoKα)=1.143 mm-1,F(000)=598,R=0.0615 and wR=0.1503 for 1752 observed reflections with I 2σ(I).The copper(II) ion in the complex adopts a slightly distorted octahedral coordination geometry and is six-coordinated with N2O4 donor set consisting of two nitrogen atoms and four oxygen atoms provided by the ligands of two imidazole molecules,two water molecules and two p-toluenesulfonate ions.The sulfonate group of the PTS ligand remains weak-coordinated and forms a number of hydrogen bonds with water molecules and imidazole ligands.X-ray structural analysis reveals that the coordination molecules are connected to form a 3-D supramolecular framework by electrostatic interaction,weak van der Waals forces,hydrogen bonding and π-π interaction.The thermal behaviour of the title complex was investigated by using DSC and TG-DTG techniques.     

Synthesis and Crystal Structure of Copper(Ⅱ)Complex with N-Acetoxyl-picolinamide

Using Cu(Ⅱ) as the template, a complex {[Cu2L2(H2O)2] 4H2O}n (L = N-acetoxyl- picolinamide) has been successfully synthesized and characterized by single-crystal X-ray diffrac tion. The crystal is of monoclinic, space group C2/c, with a = 24.144(5), b = 7.1622(14), c = 17.283(4) (A), C16H24Cu2N4O12, Mr = 591.47, β = 131.73(3)°, V = 2230.3(8) (A)3, Z = 4, Dc= 1.761 g/cm3, F(000) = 1208,μ = 1.978 mm-1, R = 0.0400 and wR = 0.1099. The copper (Ⅱ) ion is five coordinated with a distorted square pyramidal geometry. The complex can be viewed as a one dimensional chain structure by carboxylic bridges among copper atoms. In the complex there exist hydrogen bonding interactions to stabilize the structure.     

Crystal Structure,Spectroscopic Characterization,and Electrochemical and Thermal Stability Properties of a Dinuclear Nickel(Ⅱ) Complex

A new nickel(Ⅱ) complex Ni_2(L)_2(2,2?-bipy)2·5.5H_2 O with methy-bicycle[2.2.1]hept-5-ene-2,3-dicarboxylic acid(H2L) and 2,2?-bipyridine(2,2?-bipy) as ligands has been synthesized in the mixed solvent DMF and water(v:v = 5:2). It crystallizes in the triclinic space group P1 with a = 10.414(2), b = 12.884(3), c = 16.176(4) ?, α = 70.715(5), β = 80.599(5), γ = 77.383(6)o, V = 1989.4(8) ?3, Dc = 1.531 g/cm3, Z = 2, F(000) = 958, GOOF = 1.028, the final R = 0.0808 and w R = 0.2036. The crystal structure shows that the whole molecule consists of two independent dinuclear units, in which two nickel ions are bridged by two μ2-η1:η0 3-carboxylate groups of L2- anions. The coordination environment of Ni(Ⅱ) ion is Ni N_2O_3, giving a distorted square pyramidal geometry. The thermal stability and electrochemical properties of the complex were investigated.     

Synthesis,Crystal Structure and Nonlinear Optical Properties of Nickel（Ⅱ） Complex with Schiff—base Ligand

1 INTRODUCTION Recently, the transition metal complexes and inorganic clusters have also been investigated as promising nonlinear optical materials[1～3]. In our past work, much more efforts have been made to find potential nonlinear optical derived from thiosemicarbazone and dithio-carbazates[4]. As a continuous study on new nonlinear optical materials among the -electron delocalized systems con- taining mixed sulfur and nitrogen donors[5, 6], we report herein the crystal structure and…     

Electrochemical Behavior of meso-Tetra (4-Sulfonatophenyl) Porphyrin and Its Copper Complex

The complex of Cu-TPPS was formed directly by mixing equal-molar concentrations of Cu~(2+) and meso-tetra(4-sulfonatophenyl) porphyrin(TPPS)in an acetate buffer solution at pH 4-6, and its electrochemical behavior was studied by the techniques of polarography, cyclic voltammetry and spectroelectrochemistry. Three different methods were applied to accelerating the formation of Cu-TPPS in aqueous solution, i.e. heating of solution,using vitamin C as a catalyst and preadsorbing TPPS on a hanging mercury electrode. The voltammetric reductions have shown 2e~- for the first step of TPPS and 4e~- for Cu-TPPS with a peak potential at -1.04V. By applying the method of spectroelectrochemistry using a selfdesigned long-optical-path cell with Hg working electrode, the amount of saturated adsorption of TPPS and Cu-TPPS on mercury surface is found to be the same. Hence, the area of the adsorbed molecule calculated by measuring the area (i×t) under the voltammetric peak is also the same as 395 (?)~2.     

Synthesis, Crystal Structure and Thermoanalysis of o-vanillin-ethylenediamine Schiff Base Copper( Ⅱ ) Complex

The crystal structure of the title compound [Cu (o-vanillin-ethylenediamine) (H2O)] is described. The complex crystallizes in the orthorhombic system, space group Pbn21 with formula = CuC18H20N2O5, cell dimensions are: a = 0.7490(3) nm, b = 0.9256(2) nm, c=2. 4691(6) nm, V=1.712 nm3, Z = 4, Dc=l.51 g/cm3. The kinetics of thermal decomposition of the complex was studied under the non-isothermal condition by TG. Kinetic parameters were obtained from the analysis of the TG, DTG curves by integral and differential methods. By comparison of the kinetic parameters, the most probable mechanism function is f(α) = (3/2) (1-α)[-ln(1-α)]1/3, and the mathematical expression for the kinetic compensation effect is lnA = 0. 201E+0. 531.     

Crystal Structure and the Third-order Nonlinear Optical Property of a Cadmium(Ⅱ) Complex Based on a D-π-A Structural Organic Ligand

A triphenylamine-containing Schiff base ligand(L), namely, N-(4-(1 H-imidazol-1-yl)benzylidene)-N,N-diphenylbenzene-1,4-diamine, was synthesized and characterized. By coordination of the ligand with CdI2, a complex CdI2 L2 was obtained. The structure of the complex was analyzed through single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 25.277(5), b = 11.176(5), c = 17.912(5) ?, β = 106.056(5)°, V = 4863(3) ?3, Z = 4, Dc =1.633 Mg/m3, F(000) = 2360, Μr = 1195.19, μ = 1.766 mm-1, the final R = 0.0323 and wR = 0.0758 for 33414 observed reflections with I 2?(I). The linear absorption spectra of the complex were experimentally and theoretically studied. And the third-order nonlinear optical(NLO) property of the complex was also measured through Z-scan technique.     

Crystal Structure,Electrochemical and Fluorescent Properties of a New Copper(Ⅱ) Coordination Polymer with 2,3-Pyridinedi-carboxylic Acid

A new copper(Ⅱ) coordination polymer [Cu_5(Hpt)_5(H_2O)_2(2,3-PCA)2]n·12 nH_2O(1) has been successfully synthesized under hydrothermal conditions with copper hydroxide, 3-(pyridin-2-yl)-1,2,4-triazole(Hpt) and 2,3-pyridinedi-carboxylic acid(2,3-PCA). The structure of the title compound was determined by X-ray diffraction analyses, elemental analyses and IR spectrum. The architecture of 1 consists of one-dimensional sandwich-like chains which are connected by extensive hydrogen bonding interactions. The solid-state photoluminescence displays an obvious emission band at 384 nm upon excitation at 340 nm. In addition, electrochemistry property has also been studied.     

Synthesis,Crystal Structure,Spectroscopic Characterization,Thermal Stability and Magnetic Properties of a Dinuclear Copper(Ⅱ) Complex

A new copper(Ⅱ) complex [Cu2(MNA)2(2,2‘-bipy)2]·2.5H2 O with methy-5-norbornene-2,3-dicarboxylic acid(MNA) and 2,2’-bipyridine as ligands has been synthesized in the mixed solvents of DMF and water.It crystallizes in monoclinic,space group P 1,with a = 10.4191(11),b = 12.8883(13),c = 16.1114(16) ?,α = 70.8090(10),β = 80.568(2),γ = 77.440(2)o,V = 1984.3(4) ?3,Dc = 1.551 g/cm3,Z = 2,F(000) = 962,the final GOOF = 1.051,R = 0.0431 and w R= 0.0980.The crystal structure shows that the whole molecule consists of two independent dinuclear units,in which two copper ions are bridged by two μ2-η1:η0 3-carboxylate groups of MNA2-.The coordination environment of Cu(Ⅱ) ion is Cu O3N2,giving a distorted square pyramidal geometry.The spectroscopic characterization,thermal stability and magnetic properties of the complex were investigated.     

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

A new Cu(Ⅱ) complex [Cu(4-cba)(l,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 P1, a = 7.8420(2), b = 9.1070(2), c = 15.1140(6) A,α=76.889(9), β = 81.332( 11 ), γ = 74.844(11 )°, V = 1009.89(5) A3, Z = 2, Dc = 1.605 g/cm3, F(000)=498,μ=1.134 mm-1,the final R = 0.0379 and wR = 0.0865 for 2977 observed reflections with I ＞ 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.     

Syntheses,Crystal Structures,DFT Calculation and Optical Properties of a Schiff Base and Its Dinuclear Mercury(Ⅱ) Complex

A pyridine-contained Schiff base ligand L(L =(pyridine-2-vinyl)hydrazine) has been synthesized and fully characterized. By self-assembly of the ligand with HgI_2, a binuclear complex Hg_2I_4L(C) was obtained. The structures of L and C were analyzed through single-crystal X-ray diffraction. L crystallizes in monoclinic, space group P21/n with a=11.286(5), b=3.981(5), c=23.865(5) ?, β=100.043(5)°, V=1056(1) ?~3, Z=4, Dc=1.323 g/m~3, F(000)=440, Μr=210.24, μ=0.084 mm~(-1), the final R=0.0928 and w R=0.2867 for 6955 observed reflections with I 2(I). The complex is of monoclinic system, space group P21/n with a=8.706(5), b=17.468(5), c=14.675(5) ?, β=93.922(5)°, V=2227(2) ?~3, Z=4, Dc=3.338 g/m~3, F(000)=1928, Μr=1119.02, μ=19.321 mm~(-1), the final R=0.0366 and w R=0.1276 for 3920 observed reflections with I 2(I). The structural analysis revealed that the molecule of L possesses a well planar structure. However, in the complex, the coordinated ligand distorts greatly. The absorption spectra of L and the complex in ethanol were experimentally and theoretically studied. The result indicates that the complex exhibits different absorption spectrum compared with the free ligand.     

Synthesis, Crystal Structure and Optical Properties of a Cerium(Ⅳ) Complex with Chelidamic Acid

A new cerium complex,(C7H8)[Ce(C7H3NO5)2(H2O)3]·2H2O or (C7H8)[Ce(HChel)2-(H2O)3]·2H2O (1,H3Chel = 4-hydroxypyridine-2,6-dicarboxylic (chelidamic) acid),has been prepared by the hydrothermal reaction,and its crystal structure was determined based on single-crystal diffraction data. Compound 1 crystallizes in monoclinic,space group P21/c with a = 12.4267(9),b = 10.8195(7),c = 19.5650(13),β = 92.898(3)o,V = 2627.2(3) 3,Dc = 1.733 g/cm3,Z = 4,Mr = 685.55,μ = 1.809 mm-1,λ(MoKα) = 0.71073  and F(000) = 1372. The final R = 0.0455 and wR = 0.1984 for 5983 observed reflections with Ⅰ > 2σ(Ⅰ),and R = 0.0490 and wR = 0.2053 for all data. Complex 1 contains one cerium ion,two chelidamic acid ligands,three coordinated water molecules,one discrete toluene molecule,and two discrete water molecules. The Ce(IV) ion is nine-coordinate with the coordination polyhedron made up of four oxygen atoms and two nitrogen atoms from two tridentate chelating chelidamic acid ligands,and three coordinated water molecules. A three-dimensional network is formed by the H-bonds. Moreover,optical properties are investigated and the results show that this complex has sharp optical absorption at 221,396 and 571 nm but no marked fluorescent emission.     

Thiocyanate-controlled Copper(Ⅱ)-L-arginine Complex:Synthesis,Crystal Structure and Characterization

A novel thiocyanate-controlled copper(Ⅱ)-L-arginine complex with the formula of Cu(Arg)(SCN)_2(1,Arg:L-arginine) has been obtained from aqueous solution and structurally characterized by single-crystal X-ray diffraction method.Crystal data:orthorhombic,space group P2_12_12_1,a = 6.0156(5),b = 12.1905(11),c = 18.4203(16) ?,V = 1350.8(2) ?~3,Z = 4,μ = 1.933mm~(-1),F(000) = 724,S = 1.084,the final R = 0.0410,wR = 0.0754 for 1893 observed reflections with I 2σ(I),and R = 0.0559,wR = 0.0820 for all reflections.In addition,elemental analysis,IR,TG-DTG and magnetism characterization are presented.     

Synthesis and Crystal Structure of Binuclear Complex of Copper(Ⅱ)Chloroacetate with Acetamine

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A Novel Dinuclear Copper(Ⅱ) Complex: Synthesis,Crystal Structure,Properties and Hirshfeld Surface Analysis

A novel copper complex [Cu_2(L)(DMF)_2](1, H_4L =(1 Z,N?Z)-3,5-dibromo-N?-((3,5-dibromo-2-hydroxyphenyl)(hydroxy)methylene)-2-hydroxybenzohydrazonic acid which was synthesized by in-situ oxidation reaction derived from H_2hdb(H_2hdb = 6,6?-((1 E,1?E)-hydrazine-1,2-diylidenebis(methanylylidene)) bis(2,4-dibromophenol)) has been synthesized and characterized by IR, elemental analysis(CHN), TG and single-crystal X-ray diffraction. The single crystal belongs to monoclinic system, space group P21/c with a = 13.538(1), b = 3.912(1), c = 23.778(1) ?, β = 105.232(5)o, Mr = 857.08, V = 1214.9(1) ?~3, Z = 2, Dc = 2.343 g/cm~3, F(000) = 824, μ = 8.375 mm~(–1), R = 0.0566, and w R = 0.1610. Compound 1 displays weak anti-ferromagnetic interactions through a η~1:η~1:η~1:η~1:η~1:η~1:μ_2-L~(4-) bridging mode. Hirshfeld surface analysis revealed that complex 1 was supported mainly by Br···H and H···H intermolecular interactions.     

Synthesis,Crystal Structure and DNA-binding Properties of a New Copper（Ⅱ） Schiff Base Complex

A new asymmetric bidentate copper(Ⅱ) complex,CuL 2(HL=2-((E)-(4-bromophenylimino)methyl)-6-bromo-4-chlorophenol),has been synthesized and characterized by elemental analyses and single-crystal X-ray diffraction.The complex crystallizes in the monoclinic space group P2 1 /c with a=11.218(3),b=9.355(3),c=13.449(4),β=108.722(4)°,V=1336.8(6)3,Z=2,Dc=2.008 g/cm 3,μ(MoKα)=7.024 mm-1,F(000)=806,S=0.999,the final R=0.0342 and wR=0.0641for2611observed reflections (I>2σ(I)).The central copper(Ⅱ) is four-coordinate and bonds to two nitrogen and two oxygen atoms from two Schiff base ligands.The complex is linked into a two-dimensional supramolecular structure by weak intermolecular interactions.In addition,DNA-binding properties of the metal complex were investigated using spectrometric titrations and viscosity measurements.The results show that the complex binds with calf-thymus DNA(CT-DNA),presumably via a partial intercalative mode.The intrinsic binding constant of the Cu(Ⅱ) complex with DNA is 7.335×10 3 M-1.     

A Study on Complex of 1-Oxa-4,7,10-Triazacyclododecane( Ⅱ )——The Syntheses, Properties and Crystal Structure of Its Manganese( Ⅱ ) Thiocyanate Complex

Introduction The substitution of atom N for O in macrocyclic crown ether greatly influences its complexation. It is just expected that the complexing effects of the substituted macrocyclic on transition metals are greatly increased. The present paper covers the synthesis, structure and characterization of the complex [MnL(NCS)_2] of title macrocyclic ligand (L is 1-oxa-4, 7, 10-triazacy-     

Hydrothermal Synthesis, Crystal Structure and Electrochemical Properties of Complex Cu(α-Furacrylic acid)2(phen)

The title complex (C26H18CuN2O6, Mr=517.96) has been synthesized by the reaction of α-furanacrylic acid with 1,10-phenanthroline (phen) in the solvent mixture of water and methanol. Crystal data: monoclinic, space group C2/c with a=2.2927(4), b=1.01248(18), c=1.05061(18) nm, β=111.188(3)°, V=2.274(7) nm3, Dc=1.513 g/cm3, Z=4, F(000)=1060,μ=1.007mm-1, R=0.0320 and wR=0.0781. The crystal structural analysis shows that the copper atom is coordinated with four oxygen atoms from two α-furacrylic acids and two nitrogen atoms from 1,10-phenanthroline, giving a distorted octahedral coordination geometry. The result of electrochemical analysis shows that the electron transfer in the electrode reaction is quasi-reversible.