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,crystal structures and spectral properties of cobalt (Ⅱ) complexes:[ CoL (N_3) ] ·ClO_4 and CoL (N_3)_2 [L=tris ((3,5-dimethylpyrazol-1-yl) methyl) amine

Two monomeric cobalt(Ⅱ)complexes,[CoL(N3)] ClO4(1)and CoL(N3)2(2),where L is tris((3,5-dimethylpyrazol-1-yl)methyl)amine,were synthesized and their crystal structures were determined by X-ray diffraction technique.Complex 1 is five coordinated with one azide nitrogen atom and four nitrogen atoms of the tris((3,5-dimethylpyrazol-l-yl)-methyl)amine ligand,and the metal center is in distorted trigonal bipyramidal environment.Complex 2 is six coordinated distorted octahedron with the two azide nitrogen atoms and four nitrogen donors of the tris((3,5-dimethylpyrazol-1-yl)-methyl)amine ligand.The solution behaviors of the title complexes have been further investigated by UV-Vis,and 1H NMR analysis.It is found that the formation of 1 and 2 depends on the molar ratio of the azide ion to metal salt and ligand Complex 1 attached with one azide group is more stable and easy to generate than complex 2 incorporated with two azide groups,and the reasons were well discussed.     

Crystal Structures and Photoluminescence Properties of Two Lanthanide Complexes Constructed by Flexible 1,2-Phenylenediacetic Ligand

Two 3D Ln-organic coordination frameworks(Ln = Pr3+ for 1 and Er3+ for 2) have been constructed. Single-crystal X-ray diffraction analysis reveals that the two complexes have similar structures and belong to the monoclinic C2/c space group. The trans-μ4-(η2:η1)-(η1:η1) 1,2-pda2- anions link the LnIII centers to generate a 2D network containing helical motif. The dimensionality is extended into a 3D architecture through cis-bis(μ2-η2:η1) 1,2-pda2- anions linking. The geometry of Ln3+ ions is single-capped anti-square prism. Two complexes were characterized by IR spectra and thermogravimetric analysis. The solid fluorescence of 1 and 2 was also investigated at room temperature.     

Structures and Spectroscopic Properties of(1)Dipyridine Quinoxaline with Hg(Ⅱ), Cu(Ⅰ) and Ag(Ⅰ)

The interaction of Hg(Ⅱ), Cu(Ⅰ) and Ag(Ⅰ) with dipyridine quinoxaline ligand 2,3-bis(2-pyridyl)quinoxaline(DPQ) were investigated, and three new complexes have been synthesized and characterized. Complex 1 exhibits a 0D dual-core structure, complex 2 is a 0D tetra nuclear case based on a dual-core Cu unit, and complex 3 shows a one-dimensional pipeline structure. Furthermore, the optical properties of complex and DPQ were also investigated, and the results showed that the fluorescence intensity of complexes was weaker than that of ligand DPQ.     

Synthesis and Crystal Structures of Two Di-Cu(Ⅱ) Complexes Based on an Asymmetric Dinucleating Ligand

Two new dicopper(II) complexes [Cu2L(OAc)2](ClO4)·H2O(1) and [Cu2L(BPP)2]-(ClO4)(2) using an asymmetric dinucleating ligand HL and auxiliary ligands such as acetate(OAc) and bisphenyl phosphate(BPP) have been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. Complex 1 crystallizes as blue single crystals that belong to the triclinic crystal system and P1 space group, while complex 2 crystallizes in a monoclinic P21/c space group. Single-crystal X-ray diffraction analysis reveals that the two copper ions in complexes 1 and 2 reside within the adjacent ligand compartments and are bridged by the endogenous phenoxo-O from ligand L and the introduction of two desired exogenous carboxylates or phosphates in the bidentate μ-1,3-bridged mode. The coordination geometries of Cu(1) and Cu(2) are both distorted square pyramids.     

Two New Copper(Ⅱ) Complexes with p-Cyanobenzoic Acid: Synthesis,Crystal Structures and Properties

The complexes of [Cu(bpy)(H2O)(CBA)2]n 1 and [Cu(phen)(H2O)(CBA)2]·H2O 2 based on p-cyanobenzoic acid(HCBA) have been synthesized in aqueous ethanolic solution at room temperature. The single-crystal X-ray diffraction studies demonstrated that complex 1 crystallizes in orthorhombic and complex 2 is of triclinic system. The results indicate the complex 1 shows a 1D chain structure bridged by two carboxylic oxygen atoms from CBA–, and complex 2 is a mononuclear structure. Through intermolecular hydrogen bonding and π...π stacking interactions, the complexes are assembled into supramolecular structures. Complex 1 has been characterized by magnetic measurements. The magnetic measurement indicates that weak ferromagnetic interaction(zJ= 0.038(5)) between the Cu2+ ions is dominant in the structure. The IR spectrum and results of thermal and elemental analyses are also presented.     

New Copper（Ⅱ） and Nickel（Ⅱ） Complexes of 4-Morpholinoacetophenone Thiosemicarbazone： Structural, Electrochemical and Antimicrobial Studies

4-Morpholinoacetophenone thiosemicarbazone, MAPT, and its nickel（Ⅱ） and copper（Ⅱ） complexes have been prepared and characterized by elemental analysis, magnetic susceptibility, spectral methods （FT-IR, ^1H NMR） and cyclic voltammetry. Electrochemical behaviors of the complexes have been studied by cyclic voltammetry in DMF media showing metal centered reduction processes for both of them. The redox properties, nature of the electrode processes and the stability of the complexes were discussed. [Cu（MAPT）2]Cl2 complex shows Cu（Ⅱ）/Cu（Ⅰ） couple and quasi-reversible wave associated with the Cu（Ⅲ）/Cu（Ⅱ） process. The reduction/oxidation potential values depend on the structures of complexes. Also, the antimicrobial activities of these complexes were determined against S. aureus, E. coli and B. subtilis.     

Theoretical Investigations on the Structures and Properties of the Side-on Complexes B_2(N_2)_2 and Monocyclic B_n(N_2)_n~m (n=3～6,m=-1～+2)

The structures and energies of the side-on complexes B2(N2)2 and monocyclic Bn(N2)nm (n = 3～6,m = -1～+2) between N2 (1∑+g) and B (2P) have been investigated by the DFT-B3LYP and MP2 methods at the 6-311+G(2d) and aug-cc-pVTZ levels. The analyses of NICS (Nucleus Independent Chemical Shifts),NBO (nature bond orbital),AIM (atoms in molecules) and frontal orbitals have been used to reveal the origin of coordination bond between the π-electron donor N2 group and B atom,accompanied by the comparison with the end-on complexes. The results have indicated that the side-on coordination complexes can be formed due to the relative strong fluidity of the π-electrons,and the nature of the coordination bond has been exposed to be that the N2 group offers 1πu electron to the 2p orbital of boron. The coordinate energies of the side-on complexes are less than those of the end-on complexes. Furthermore,the aromaticity of side-on coordination complex is weaker than that of the corresponding end-on coordination complex.     

Synthesis, Crystal Structure, Fluorescence Property and Antibacterial Activity of Two Unprecedented One-dimensional Chain Metal organic Coordination Polymers： Zn（H-SSA）（Phen）（H20）2 and Cu（H-SSA） （Phen） （H20）2

The reaction of 5-sulfosalicylic acid(H3-SSA) with o-phenanthroline(Phen),NaOH,and Mcl2(M=Zn,Cu) affords Zn(H-SSA)(Phen)(H2O)2(1) and Cu(H-SSA)(Phen)(H2O)2 (2),respectively ,compounds 1 and 2 are characterized by elemental analysis,IR,fluorescence spectra and single crystal Xray diffraction analysis.The X-ray diffraction analyses reveal that compounds 1 and 2 are isostructure.The 5-sulfosalicylic acid ligand loses two protons at the sulfo-group and carboxylic group during the reaction.The Zn(II) and Cu(II)ions are sixcoordinated and adopt distorted octahedral geometry,which are surrounded by two N atoms from Phen,two O atoms from two water molecules,one O atom from-SO3 group and one oxygen from carboxylic group of the other H-SSA.Compounds 1 and 2 have unprecedented one-dimensional linear chain formed by a repeating mononuclear structureal unit.which is bridged by H-SSA.The fluorescence intensity of 1 and 2 is stronger than that of Phen and H3-SSA at 400nm.The lowest excited single states of these complexes are assigned as mainly Phen localized 1(π π),The antibacterial activity test shows that compounds 1 and 2 strongly inhibit the growth of Streptococcus haemolyticus,Straphylococcus aureus and Escherichia coli.     

Synthesis, Characterization and the Effect of Glucose-lowering of Guanidino Acid Oxovanadium（Ⅳ） Complexes

Two guanidino acid oxovanadium(Ⅳ) complexes have been synthesized. Preliminary tests in vivo have shown that the two title complexes all display lowering glucose activity in vivo to STZ-rats. The effect of glucose-lowering of guanidino acetic acid oxovanadium(Ⅳ) complex in vivo is higher than that of guanidino propanoic acid oxovanadium(Ⅳ) complex.     

Synthesis of New Ruthenium（Ⅱ）Bipyridyl Complexes and Studies on Their Photophysical and Photoelectrochemical Properties

Two new mixed-ligand ruthenium(Ⅱ） complexes,Ru(dcbpy)-(LL)NCS)2[where dcbpy=4,4‘-dicarboxyl-2,2‘‘-bipyridine,LL=4,4‘-bis(N-methyl-anilinomethyl)-2,2‘‘-bipyridine(2)],were synthesized,and the tphotophysical properties of these complexes were studied.The metal-to-ligand charge transfer (MLCT) transitions of these complexes exhibited solvatochromic effect due to the existence of NCS ligands.The MLCT energies also strongly depend on the pH values of the solutions because of protonation and deprotonation of the carboxyl groups.The pKa values of the ground state,4.0 for 1 and 3.8 for 2,were obtained from the titration curves.The photoelectrochemical properties of 1 and 2 as sensitizers in sandwich-type solar cells have been studied.Complex 1 exhibited better photoelectrochemical behavior than complex 2 as expected.It was proved that the design of mixed-ligand complex by introducing electron donating group in one of the ligands should be a promising approach.     

Syntheses,Crystal Structures and Intermolecular Interactions of Cu（II） Complexes with Methyl- benzoic Acid （MBA） and 1,10-Phenanthroline

Two cupric complexes containing methylbenzoic acid have been prepared and crystallized by solvent evaporation method in DMF. The single-crystal X-ray crystallographic analysis reveals that they are dicaryon complexes. Complex I with formula of [Cu2（m- MBA）4DMF2] crystallizes in monoclinic with space group of P21/c and complex 2 with formula of [Cuz（o-MBA）ffo-phen）2]·NO3·H2O crystallizes in triclinic with space group of P I. The weak interactions including C-H...O hydrogen bonds, C-H…π interactions and π-π stacking in the structures of two complexes are observed from the X-ray crystallographic data. In addition, there are still classical hydrogen bonds in 2. The different strength of intermolecular interaction in the structure is reflected on their different thermal stability measured by thermal gravimetric analysis and 2D-1R correlation spectroscopy of two complexes. The study of weak interactions is meaningful to provide supporting data for supramolecular chemistry theory and potential applications in molecular biology.     

Syntheses and Crystal Structures of Cd(Ⅱ) and Ni(Ⅱ) Complexes Containing Flexible Sulfide and Nitrogen Heterocyclic Ligands

Two new coordination polymers [Cd(EBLA)(ip)(H2O)](1) and [Ni(EBSA)(im)2(H2O)]n(2) were synthesized by hydrothermal and solution methods using 2,2'-dithiosalicylicacid(EBSA), 1H-imidazo[4,5-f][1,10]phenanthroline(ip), imidazole(im), Cd(NO3)2·4H2O and Ni(NO3)2·6H2O. The complexes were characterized by elemental analysis and FT-IR. Meanwhile, the crystal structures, fluorescence properties of complex 1 and thermogravimetrie analysis of complex 2 have been studied. In complex 1, 2,2'-dicarboxydiphenylthioether(EBLA) was prepared with 2,2'-dithiosalicylicacid(EBSA) in situ reaction by hydrothermal method. Complex 1 is a dinuclear structure and Cd2+ is five-coordinated in a distorted trigonal bipyramidal geometry. Complex 2 is a one-dimensional infinite linear chain and Ni2+ is six-coordinated to form a distorted octahedral geometry. Hydrogen bonding and π-π interactions are observed in these complexes.     

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, 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.     

Crystal Structure and Property Research on Compounds Co（Ⅱ） and Zn（Ⅱ） with 3-Methylbenzoic Acid

Two compounds with 3-methylbenzoic acid(HL) [Co(L)2(4,4'-bipy)]n 1 and [Zn2(L)4(4,4'-bipy)]n 2(L = 3-methylbenzoic acid) have been hydrothermally synthesized directly and characterized by single-crystal X-ray diffraction analysis,elemental analyses,IR spectra and ultraviolet-visible diffuse reflection integral spectra(UV-Vis DRIS).The two compounds are both one-dimensional infinite chains.The structural difference is that 1 is a double-chain structure and 2 is only a single chain one.At the same time,the carboxylate groups adopt different modes in the two compounds,relatively.Additionally,in order to explore the structural characteristic,two-dimen-sional IR spectra are investigated for 1 and 2.Photo-luminescent property of 2 is also researched in detail.     

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.     

Syntheses,Crystal Structures and Magnetic Properties of Two Nitrophenyl Substituted Nitronyl Nitroxide Radical-lanthanide Complexes

Syntheses, structures and magnetic properties of two nitrophenyl substituted nitronyl nitroxide radical-lanthanide complexes [Ln(hfac)3(NITmNO_2)2](Ln = Sm(ⅡI)(1), Tb(ⅡI)(2), hfac = hexafluoroacetylacetonate, NITmNO_2 = 2-(3-nitrophenyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide) have been described in this paper. X-ray analysis shows that the two complexes have similar mononuclear trispin radical-Ln(ⅡI)-radical structures, in which the central Ln(ⅡI) ions are all eight coordinated in D2 d dodecahedral(DD) geometry formed by six oxygen atoms from three hfac and two oxygen atoms from nitronyl nitroxide. The magnetic study indicates the antiferromagnetic interaction between Sm(ⅡI) ion and NITmNO_2 in complex 1, while weak ferromagnetic interaction between Tb(ⅡI) ion and NITmNO_2 in complex 2.     

Synthesis, DNA-binding and photocleavage studies of ruthenium(Ⅱ) complexes [Ru(btz)_3]~(2+) and [Ru(btz)(dppz)_2]~(2+)

Two new ruthenium(Ⅱ) complexes, [Ru(btz)3](ClO4)2 (1) and [Ru(btz)(dppz)2](ClO4)2 (2) (btz = 4,4′-bithi-azole, dppz = dipyrido[3,2-a:2′,3′-c]phenazine), have been synthesized and characterized by elemental analysis, 1H NMR, ES-MS and X-ray crystallography. The DNA binding behaviors of two complexes have been studied by spectroscopic and viscosity measurements. The results suggest that complex 1 binds to CT-DNA via an electrostatic mode, while complex 2 via an intercalative mode. Under irradiation at 365 nm,...     

Synthesis,Crystal Structures and Properties of Two Novel Co（Ⅱ） and Cd（Ⅱ） Complexes of N-AcetyI-L-glutamic Acid and Imidazole Ligands

Two novel complexes {[Co（A-glu）（Im）2]·0.5H2O}n （1） and [Cd（A-glu）（Im）3]n （2） （H2A-glu=N-acetyl-L-glutamic acid, Im=imidazole） have been synthesized from the reaction of H2A-glu with Co（CH3COO）2·4H2O or Cd（CH3COO）2·2H2O in the presence of Im. Both of the complexes display different coordination environment and similar one-dimensional chain structure. The magnetic susceptibility measurements for 1 show a weak antiferromagnetic interaction between two cobalt（Ⅱ） ions bridged by A-glu ligand. The complex 2 exhibits an intense fluorescent emission in solid state at room temperature.