Two zinc（II） complexes, namely, [Zn（L1）Cl2]2 （1） and {[Zn（L2）（tbta）]·3H2O}n （2） （L1 = 1,3-bis（2-methylbenzimidazol-1-ylmethyl）benzene, H2tbta = tetrabromoterephthalic acid, L2 = 1,3-bis（2-methylbe...Two zinc（II） complexes, namely, [Zn（L1）Cl2]2 （1） and {[Zn（L2）（tbta）]·3H2O}n （2） （L1 = 1,3-bis（2-methylbenzimidazol-1-ylmethyl）benzene, H2tbta = tetrabromoterephthalic acid, L2 = 1,3-bis（2-methylbenzimidazol-1-yl）-2-propanol） have been successfully obtained under hydrothermal conditions. Complex 1 displays binuclear structure which is further extended into a 1D supramolecular chain through π–π stacking. Complex 2 features 2D （4,4） network based on L2/tbta2– double linker. The thermal stability, fluorescence properties and catalytic activities of two complexes for degradation of Methyl orange in a Fenton-like process were discussed.展开更多
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...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.展开更多
[Zn（L）（CH3OH）3]（H2L = N-（1-phenyl-3-methyl-4-propenylidene-5-pyrazolone）-salicylidene hydrazide） has been synthesized by the reaction of zinc nitrate and ligand H2 L. The complex crystallizes in orthorhombic s...[Zn（L）（CH3OH）3]（H2L = N-（1-phenyl-3-methyl-4-propenylidene-5-pyrazolone）-salicylidene hydrazide） has been synthesized by the reaction of zinc nitrate and ligand H2 L. The complex crystallizes in orthorhombic system, space group Pbca with a = 5.888（15）, b = 14.564（14）, c = 22.20（2） , V = 5137（8） 3, Z = 8 and F（000） = 2184. The ligand serves as a negative bivalent tridentate chelating agent to coordinate with the central zinc（II） atom. DNA-binding was studied by UV-Vis spectral analysis and ethidium bromide（EB） displacement experiments. The results showed that the DNA-binding constant of the complex is 5.1×104 M–1. Antitumor activity of [Zn（L）（CH3OH）3] and the ligand have been investigated by MTT assay, which indicated that the complex has better cytotoxicity to Eca-109 and He La than free ligand.展开更多
Under hydrothermal conditions, 4-（4,5-dicarboxy-lH-imidazol-2-yl）pyridine 1-oxide （H3DCImPyO） reacted with ZnC12 to give the 1D chain complex {[Zn（DCImPyO）·（H2O）2·]·H3O}n （1）. Single-crystal ...Under hydrothermal conditions, 4-（4,5-dicarboxy-lH-imidazol-2-yl）pyridine 1-oxide （H3DCImPyO） reacted with ZnC12 to give the 1D chain complex {[Zn（DCImPyO）·（H2O）2·]·H3O}n （1）. Single-crystal X-ray determination shows that complex 1 crystallizes in the monoclinic system, space group P21/c with a = 9.488（2）, b = 13.247（3）, c = 12.959（4） A, β = 126.716（19）°, Z = 4, V= 1305.6（6）/k3, C10H11N3O8Zn, Dc = 1.865 g/cm3, Mr = 366.61, 2（MoKa） = 0.71073 A, μ= 1.930 mm1, F（000） = 744, R = 0.0472 and wR = 0.1487. Fluorescent analysis showed an intense emission band at 422 nm when the exciting radiation was set at 378 nm. Dielectric constant of complex 1 was measured at different frequencies with temperature variation.展开更多
The structure of a zinc（Ⅱ） coordination complex（1）, [C14 H10 N3 O5 Zn1.5]n or [Zn1.5（bzim）（pydc）（H2 O）]n（H2 pydc = pyridine-2,3-dicarboxylic acid, Hbzim = benzimidazole）, has been determined by X-ray crys...The structure of a zinc（Ⅱ） coordination complex（1）, [C14 H10 N3 O5 Zn1.5]n or [Zn1.5（bzim）（pydc）（H2 O）]n（H2 pydc = pyridine-2,3-dicarboxylic acid, Hbzim = benzimidazole）, has been determined by X-ray crystallography and characterized by elemental analysis, IR spectrum and luminescence. Chemical formula： C14 H10 N3 O5 Zn1.5. It crystallizes in the monoclinic system, space group P21/c with a = 12.303（4）, b = 12.052（4）, c = 10.212（3） ？, β = 104.147（4）, V = 1468.3（8） ？3, Z = 4, Mr = 398.30, Dc = 1.802 g/cm3, F（000） = 800, μ = 2.501 mm-1 and S = 1.000. The 2-D network architecture of 1 is constructed from benzimidazole, zinc and pyridine-2,3-dicarboxylic acid. The quantum-chemical calculations have been performed on ‘molecular fragments’ extracted from the crystal structure using the B3 LYP method in Gaussian 09. The luminescence spectrum shows that complex 1 emits blue luminescence.展开更多
A new complex has been synthesized with o-methylbenzoyl-benzoic acid（HL） and 1,10-phenanthroline（phen） in the mixture of water and ethanol. It crystallizes in monoclinic, space group C2/c with a = 13.6328（18）, b...A new complex has been synthesized with o-methylbenzoyl-benzoic acid（HL） and 1,10-phenanthroline（phen） in the mixture of water and ethanol. It crystallizes in monoclinic, space group C2/c with a = 13.6328（18）, b = 17.7876（18）, c = 19.998（2）, β = 104.720（4）o, C54H48N4O11Zn, Mr = 994.33, V = 4690.2（9）3, Dc = 1.408 g/cm3, Z = 4, F（000） = 2072, μ（MoKα） = 0.59 mm-1, R = 0.0736 and wR = 0.2029. The crystal structure shows that the zinc ions are coordinated with two oxygen atoms from two HL molecules and four nitrogen atoms from two phen molecules, forming distorted octahedral coordination geometry. The fluorescent and thermal stability properties of the complex are studied. The result shows that it has one fluorescent emission band at around 412 nm. In addition, the complex is stable under 210 ℃.展开更多
A novel polymeric zinc（II） complex {[Zn2（TIA）（H2O）3]·（NO3）}n（1, H3TIA = 5-（1H-tetrazol-5-yl）isophthalic acid） has been synthesized in mixed solvents under solvothermal conditions and characterized by ...A novel polymeric zinc（II） complex {[Zn2（TIA）（H2O）3]·（NO3）}n（1, H3TIA = 5-（1H-tetrazol-5-yl）isophthalic acid） has been synthesized in mixed solvents under solvothermal conditions and characterized by elemental analysis, IR spectroscopy and X-ray single-crystal diffraction. Complex 1 crystallizes in orthorhombic, space group Cmcm with a = 10.4210（6）, b =23.3526（14）, c = 6.9214（4）A, V = 1684.37（17）A^3, Z = 4, C9H4N5O（10）Zn2, Mr = 472.91, Dc = 1.865g/cm^3, F（000） = 932, λ（MoK α） = 2.909 mm^-1, R = 0.0423 and wR = 0.1287. The complex has good thermal stability and excellent photoluminescent property.展开更多
The self-assembly of clusters in inorganic systems is an interesting subject. The self-assembly of big molecules has been well established in biological systems. In addition, the coordination chemistry of metal-sulfur...The self-assembly of clusters in inorganic systems is an interesting subject. The self-assembly of big molecules has been well established in biological systems. In addition, the coordination chemistry of metal-sulfur-nitrogen cluster complexes has been a very active and attracting field for many years as a result of the novelty and versatility of the crystal structures and reactivities of such clusters, as well as their potential applications as the models for the active sites in non-heme proteins. At the same time, there is currently considerable interest in the formation of metal complexes with heterocyclic ligands because of the diverse characteristics of ligands and their consequential wide range of applications.展开更多
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 [Z...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.展开更多
A new tetranuclear zinc（II） complex [Zn4（SO4）2（DPPZ）4（HSal）2（OH）2] 1 （DPPZ = dipyrido[3,2-a：2＇,3＇-c]phenazine, H2Sal = salicylic acid） was prepared by using hydrothermal synthesis and characterized by e...A new tetranuclear zinc（II） complex [Zn4（SO4）2（DPPZ）4（HSal）2（OH）2] 1 （DPPZ = dipyrido[3,2-a：2＇,3＇-c]phenazine, H2Sal = salicylic acid） was prepared by using hydrothermal synthesis and characterized by elemental analysis, IR spectrum, thermal gravimetry （TG）, fluorescent emission and single-crystal X-ray diffraction. Its crystal structure is of monoclinic, space group P2 1/c with a = 9.8897（8）, b = 14.2506（12）, c = 26.384（2） ,A, β = 94.8940（10）°, V = 3704.8（5） A3 Z = 2, C86H52N16O16S2Zn4, Mr = 1891.04, Dc = 1.695 g/cm^3, μ= 1.423 mm^-1, F（000） = 1920, GOOF = 1.039, the final R = 0.0358 and wR = 0.0872 for 6038 observed reflections with I 〉 2σ（I）. In 1, ＂cage-like＂ tetranuclear clusters of [Zn4（SO4）2（DPPZ）4（HSal）2（OH）2] are further stacked through π-π interactions to generate a 3D supramolecular network.展开更多
The title complex is a new binuclear Zn(Ⅱ) with chelate ligand of Schiff base containing S and N atom.The complex crystallizes in the orthorhombicspace group Pccn,with a=12.338(9),b=16.666(8),c=17.503(6),V=3599(6),Mr...The title complex is a new binuclear Zn(Ⅱ) with chelate ligand of Schiff base containing S and N atom.The complex crystallizes in the orthorhombicspace group Pccn,with a=12.338(9),b=16.666(8),c=17.503(6),V=3599(6),Mr=723.52,Z=4,Dx=1.34 g/cm3,μ=15.22 cm-1,F(000)=1488.The structure was solved by direct methods and the final R=0.078.The crystal consists of discrete molecules with symmetric center at the center of the fourmembered ring consisting of two Zn atoms and two O atoms.展开更多
A homochiral complex, Zn3（Hsalen）2（Py）4（H2O）2 （salen = （1R,2R）-（-）-diamino-cyclohexane-N,N＇-biscarboxyl-salicylidene） 1, has been synthesized by solvothermal procedure and characterized by IR, microanalys...A homochiral complex, Zn3（Hsalen）2（Py）4（H2O）2 （salen = （1R,2R）-（-）-diamino-cyclohexane-N,N＇-biscarboxyl-salicylidene） 1, has been synthesized by solvothermal procedure and characterized by IR, microanalysis, TGA, powder and single-crystal X-ray crystallography. It crystallizes in monoclinic space group P2 with a = 10.9439（7）, b = 10.1722（6）, c = 27.3450（17）, β = 97.5060（10）o, V = 3018.1（3） 3, Z = 2, Zn3（Hsalen）2（Py）4（H2O）2, Mr = 1363.33, Dc = 1.500 g/cm3, F（000） = 1408, μ = 1.257 mm-1, GOOF = 1.042, the final R = 0.0601 and wR = 0.1464 for 10322 observed reflections with I 2σ（I）. The coordination polymer 1 possesses a 1D infinite zigzag chain architecture constructed by strong hydrogen bonding interactions and the polymeric chains are further assembled into a 2D supramolecular network structure via C–H···π interactions between the cyclohexane and aromatic rings of the ligand of adjacent chains. Simultaneously, π···π stacking interactions play an important role in forming the 2D supramolecular framework.展开更多
A new trinuclear zinc complex Zns（2,2＂-bipy）2（3,5-DMBA）6＂（H20）1.5 （1） with 3,5-dimethylbenzoic acid （3,5-DMBA） and 2,2＂-bipyridine as ligands has been synthesized in the mixed solvents of methanol and wat...A new trinuclear zinc complex Zns（2,2＂-bipy）2（3,5-DMBA）6＂（H20）1.5 （1） with 3,5-dimethylbenzoic acid （3,5-DMBA） and 2,2＂-bipyridine as ligands has been synthesized in the mixed solvents of methanol and water. It crystallizes in the monoclinic space group C2/c with a = 31.1497（15）, b = 11.7576（6）, c = 20.9049（10） A, fl = 118.4550（10）°, V- 6731.4（6） A3, Dc = 1.412 g/cm3, Z = 4, F（000） = 2972, GOOF = 1.069, the final R= 0.0667 and wR= 0.1917. The whole molecule consists of three zinc ions, six 3,5-DMBA molecules, two 2,2＂-bipyridine molecules and one and half water molecules, in which three zinc ions are bridged by six μ2-η1：η0 carboxylate groups of 3,5-DMBA. The Zn（1） atom is centrosymmetric, and adopts a distorted octahedral ZnO6 geometry, while the Zn（2） gives a distorted square pyramidal ZnOsN2 geometry. The spectroscopic characterization and thermal stability properties of the complex were investigated.展开更多
Two new ternary complexes [Zη（3-aba）2（phen）]·2.58H2O 1 and {[Cd（3-aba）- （phen）2]·（NO3）·（1.5H2O） }n 2 （3-aba = 3-aminobenzoic acid anion, phen = 1,10-phenanthroline） were synthesized and c...Two new ternary complexes [Zη（3-aba）2（phen）]·2.58H2O 1 and {[Cd（3-aba）- （phen）2]·（NO3）·（1.5H2O） }n 2 （3-aba = 3-aminobenzoic acid anion, phen = 1,10-phenanthroline） were synthesized and characterized by elemental analysis, IR, UV spectrum and X-ray diffraction. Complex 1 crystallizes in the rhombohedral system, space group R3 with a = 3.5733（3）, b = 3.5733（3）, c = 1.1231（2） nm; V= 12.419（3） nm^3, C26H25.17NaO6.58Zn, Mr= 564.37, Z= 18, F（000） = 5253, μ= 0.937 mm^-1, Dc = 1.358 g/cm^3, R = 0.0668 and wR = 0.1690 for 2424 observed reflections （I〉 2σ（I））. Complex 2 belongs to the tetragonal system, space group P4/ncc with a = 2.88451（10）, b = 2.88451（10）, c = 1.55571（11） nm, V= 12.9441（11） nm^3, C31H25CdN6O6.50, Mr = 697.97, Z = 16, F（000） = 5648,μ=0.727 mm^-1, Dc= 1.433 g/cm^3, R = 0.0607 and wR = 0.1742 for 3468 observed reflections （I 〉 2σ（I））. Complex 1 displays a mononuclear structure. The carboxylate group of 3-aminobenzoic acid anion coordinates to Zn（Ⅱ） in a chelating bidentate mode, and the nitrogen atom of the ligand does not involve in coordination. Complex 2 exhibits a one-dimensional chain structure with 3-aminobenzoic acid anion coordinating to Cd（Ⅱ） in a μ2-bridging mode through its nitrogen atom and one of its oxygen atoms.展开更多
Reaction of Zn(ClO4)2·6H2O with septadentate 2,6-bis[bis(2-benzimidazolylme-thyl)amino methyl]-4-methylphenol (Hbbap) and sodium isonicotinate yielded a dinuclear zinc complex[Zn2(bbap) (Iso) (Hiso)] (ClO4)2·...Reaction of Zn(ClO4)2·6H2O with septadentate 2,6-bis[bis(2-benzimidazolylme-thyl)amino methyl]-4-methylphenol (Hbbap) and sodium isonicotinate yielded a dinuclear zinc complex[Zn2(bbap) (Iso) (Hiso)] (ClO4)2·[Zn2 (bbap) (Iso) (H2O)] (ClO4)2·4H2O(1a·1b·4H2O). Hiso isisonicotinic acid and Iso is isonicotinate anion. The structure has been established by X-raycrystallography and shows that the two zinc ions are bridged by the phenoxy unit of bbap- ligand,and the presence of unusual monodentate O-coordination of carboxylate group from isonicotinicacid. The coordination geometry around the zinc ion is approximately trigonal bipyramidal.展开更多
A novel zinc（II） complex, Zn（IBT）2 （1, H1BT = 5-（4-（（1H-imidazol-1-yl）methyl）- phenyl）-2H-tetrazole） has been synthesized with Zn（NO3）2·6H2O, 4-（imidazol-l-ylmethyl）benzonnitrile （IBN） and NaN3 ...A novel zinc（II） complex, Zn（IBT）2 （1, H1BT = 5-（4-（（1H-imidazol-1-yl）methyl）- phenyl）-2H-tetrazole） has been synthesized with Zn（NO3）2·6H2O, 4-（imidazol-l-ylmethyl）benzonnitrile （IBN） and NaN3 by the hydrothermal method, and characterized by elemental analysis, IR and single-crystal X-ray diffraction. Crystallographic data for 1： C22H18N12Zn, Mr = 515.85, orthorhombic, Pbcn, a = 16.0567（15）, b = 9.5316（9）, c = 14.6107（14） A, V= 2236.1（4） A3, Z= 4, Dc = 1.532 g/cm3,μ = 1.138 mm-1, F（000） = 1056, R = 0.0350 and wR = 0.0888 for 1438 observed reflections （I 〉 2σ（I）） and the goodness-of-fit S = 1.002 on F2. The crystal structural analysis revealed that complex 1 exhibits a rare two-dimensional homochiral wave-like layer structure. In addition, the photoluminescence of complex 1 was studied in the solid state at room temperature together with its theoretical analysis.展开更多
Compounds with visible-light-induced photoluminescence are particularly attractive in acting as the emitting components of light-emitting diodes and fluorescent probes for biological applications. A new complex [Zn(NC...Compounds with visible-light-induced photoluminescence are particularly attractive in acting as the emitting components of light-emitting diodes and fluorescent probes for biological applications. A new complex [Zn(NCS)_3(MQ)](MQ^+ = N-methyl-4,4?-bipyridinium) with an isolated molecular structure has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy and solid-state photoluminescent determination. Crystal data: C_(14)H_(11)N_5S_3Zn, M_r = 410.83, monoclinic, space group P2_1/c, a = 8.809(5), b = 13.138(7), c = 15.580(9) ?, b = 104.433(10)°, V = 1746.2(17) ?~3, Z = 4, D–c = 1.563 g×cm^3, μ = 1.769 mm^(–1), F(000) = 832, the final R = 0.0376 and wR = 0.1243 for 2850 observed reflections with I > 2s(I). In the crystal structure, the zinc atom is tetrahedrally coordinated by one MQ+ ligand and three NCS– groups to yield a tetrahedral configuration. The bond length of Zn–NMQ is clearly shorter than those found in reported Zn(Ⅱ) complexes of 4,4?-bipy. The isolated units are joined by C–H···S interactions to generate a 2D hydrogen-bonding network. This compound displays visible light-induced photoluminescence, which originates from both intraligand charge-transfer of the MQ+ ligand and NCS~–→MQ^+ charge-transfer according to a density of states(DOS) calculation. Moreover, its emission band shows a clear blue shift compared with those of halide compounds.展开更多
基金Supported by the National Natural Science Foundation of China(No.51474086)Natural Science Foundation-Steel and Iron Foundation of Hebei Province(B2015209299)Undergraduate Innovation Programs of North China University of Science and Technology(No.X2015004)
文摘Two zinc（II） complexes, namely, [Zn（L1）Cl2]2 （1） and {[Zn（L2）（tbta）]·3H2O}n （2） （L1 = 1,3-bis（2-methylbenzimidazol-1-ylmethyl）benzene, H2tbta = tetrabromoterephthalic acid, L2 = 1,3-bis（2-methylbenzimidazol-1-yl）-2-propanol） have been successfully obtained under hydrothermal conditions. Complex 1 displays binuclear structure which is further extended into a 1D supramolecular chain through π–π stacking. Complex 2 features 2D （4,4） network based on L2/tbta2– double linker. The thermal stability, fluorescence properties and catalytic activities of two complexes for degradation of Methyl orange in a Fenton-like process were discussed.
基金Supported by the Scientific and Technological Program of Hunan Provincial Department of Science and Technology (No. 2010JT4041)Hunan Provincial Department of Education (No. 11C0186)Hunan Provincial Key Discipline Construction and Hunan College Key Laboratory of Functional Organometallic Materials
文摘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.
基金Supported by the National Science Foundation of China(No.21161019,21301146)Natural Science Fund for Distinguished Young Scholars of Xinjiang Uygur Autonomous(No.2013711008)Technological Innovation Youth Training Project of Xinjiang Autonomous(No.2013721017)
文摘[Zn（L）（CH3OH）3]（H2L = N-（1-phenyl-3-methyl-4-propenylidene-5-pyrazolone）-salicylidene hydrazide） has been synthesized by the reaction of zinc nitrate and ligand H2 L. The complex crystallizes in orthorhombic system, space group Pbca with a = 5.888（15）, b = 14.564（14）, c = 22.20（2） , V = 5137（8） 3, Z = 8 and F（000） = 2184. The ligand serves as a negative bivalent tridentate chelating agent to coordinate with the central zinc（II） atom. DNA-binding was studied by UV-Vis spectral analysis and ethidium bromide（EB） displacement experiments. The results showed that the DNA-binding constant of the complex is 5.1×104 M–1. Antitumor activity of [Zn（L）（CH3OH）3] and the ligand have been investigated by MTT assay, which indicated that the complex has better cytotoxicity to Eca-109 and He La than free ligand.
基金Supported by the Natural Science Foundation of Jiangsu Province(BK2008029)the Foundation of Jiangsu Educational Committee(11KJB150004)
文摘Under hydrothermal conditions, 4-（4,5-dicarboxy-lH-imidazol-2-yl）pyridine 1-oxide （H3DCImPyO） reacted with ZnC12 to give the 1D chain complex {[Zn（DCImPyO）·（H2O）2·]·H3O}n （1）. Single-crystal X-ray determination shows that complex 1 crystallizes in the monoclinic system, space group P21/c with a = 9.488（2）, b = 13.247（3）, c = 12.959（4） A, β = 126.716（19）°, Z = 4, V= 1305.6（6）/k3, C10H11N3O8Zn, Dc = 1.865 g/cm3, Mr = 366.61, 2（MoKa） = 0.71073 A, μ= 1.930 mm1, F（000） = 744, R = 0.0472 and wR = 0.1487. Fluorescent analysis showed an intense emission band at 422 nm when the exciting radiation was set at 378 nm. Dielectric constant of complex 1 was measured at different frequencies with temperature variation.
基金Supported by the Jilin Province Science and Technology Development Plan Item(No.20140204080GX)the Project of the Education Department of Jilin Province,China(No.JJKH20180777KJ)the Science and Technology Development Projects of Siping City(No.2017057)
文摘The structure of a zinc（Ⅱ） coordination complex（1）, [C14 H10 N3 O5 Zn1.5]n or [Zn1.5（bzim）（pydc）（H2 O）]n（H2 pydc = pyridine-2,3-dicarboxylic acid, Hbzim = benzimidazole）, has been determined by X-ray crystallography and characterized by elemental analysis, IR spectrum and luminescence. Chemical formula： C14 H10 N3 O5 Zn1.5. It crystallizes in the monoclinic system, space group P21/c with a = 12.303（4）, b = 12.052（4）, c = 10.212（3） ？, β = 104.147（4）, V = 1468.3（8） ？3, Z = 4, Mr = 398.30, Dc = 1.802 g/cm3, F（000） = 800, μ = 2.501 mm-1 and S = 1.000. The 2-D network architecture of 1 is constructed from benzimidazole, zinc and pyridine-2,3-dicarboxylic acid. The quantum-chemical calculations have been performed on ‘molecular fragments’ extracted from the crystal structure using the B3 LYP method in Gaussian 09. The luminescence spectrum shows that complex 1 emits blue luminescence.
基金Supported by the Natural Science Foundation of Hunan Province(No.11JJ9006)Key Project of Science and Technology Plan of Hunan Province(2012FJ2002)the Construct Program of the Key Discipline in Hunan Province
文摘A new complex has been synthesized with o-methylbenzoyl-benzoic acid（HL） and 1,10-phenanthroline（phen） in the mixture of water and ethanol. It crystallizes in monoclinic, space group C2/c with a = 13.6328（18）, b = 17.7876（18）, c = 19.998（2）, β = 104.720（4）o, C54H48N4O11Zn, Mr = 994.33, V = 4690.2（9）3, Dc = 1.408 g/cm3, Z = 4, F（000） = 2072, μ（MoKα） = 0.59 mm-1, R = 0.0736 and wR = 0.2029. The crystal structure shows that the zinc ions are coordinated with two oxygen atoms from two HL molecules and four nitrogen atoms from two phen molecules, forming distorted octahedral coordination geometry. The fluorescent and thermal stability properties of the complex are studied. The result shows that it has one fluorescent emission band at around 412 nm. In addition, the complex is stable under 210 ℃.
基金Supported by the National Natural Science Foundation of China(No.21576112)the Program for New Century Excellent Talents in University(NCET-10-0176)of ChinaNatural Science Foundation Project of Jilin Province(No.20130521019JH and 201215219)
文摘A novel polymeric zinc（II） complex {[Zn2（TIA）（H2O）3]·（NO3）}n（1, H3TIA = 5-（1H-tetrazol-5-yl）isophthalic acid） has been synthesized in mixed solvents under solvothermal conditions and characterized by elemental analysis, IR spectroscopy and X-ray single-crystal diffraction. Complex 1 crystallizes in orthorhombic, space group Cmcm with a = 10.4210（6）, b =23.3526（14）, c = 6.9214（4）A, V = 1684.37（17）A^3, Z = 4, C9H4N5O（10）Zn2, Mr = 472.91, Dc = 1.865g/cm^3, F（000） = 932, λ（MoK α） = 2.909 mm^-1, R = 0.0423 and wR = 0.1287. The complex has good thermal stability and excellent photoluminescent property.
基金Supported by the National Natural Science Foundation of China(Nos. 20476011 and 20371007).
文摘The self-assembly of clusters in inorganic systems is an interesting subject. The self-assembly of big molecules has been well established in biological systems. In addition, the coordination chemistry of metal-sulfur-nitrogen cluster complexes has been a very active and attracting field for many years as a result of the novelty and versatility of the crystal structures and reactivities of such clusters, as well as their potential applications as the models for the active sites in non-heme proteins. At the same time, there is currently considerable interest in the formation of metal complexes with heterocyclic ligands because of the diverse characteristics of ligands and their consequential wide range of applications.
基金supported by the Project for Undergraduate Research Study and Innovative Experiment of Hunan Provincial(2013-191)National Undergraduate Training Programs for Innovation and Entrepreneurship(201310551158)+4 种基金the Scientific Research Fund of Hunan Provincial Education Department(13B029,13A030)the Key Laboratory of Functional Organometallic Materials of Hunan Province College(13K09,13K10)the Program for Excellent Talents in Hunan University of Science and Engineeringthe Construct Program of the Key Discipline in Hunan Province(2011-76)the Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province(2012-318)
文摘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.
基金Supported by the Natural Science Foundation of Jilin Province (No. 20060516)the Doctoral Foundation of Jilin Normal University (No. 2006006 and No. 2007009)+1 种基金the Science and Technology Institute Foundation of Siping City (No. 2005016)the Subject and Base Construction Foundation of Jilin Normal University (No. 2006041)
文摘A new tetranuclear zinc（II） complex [Zn4（SO4）2（DPPZ）4（HSal）2（OH）2] 1 （DPPZ = dipyrido[3,2-a：2＇,3＇-c]phenazine, H2Sal = salicylic acid） was prepared by using hydrothermal synthesis and characterized by elemental analysis, IR spectrum, thermal gravimetry （TG）, fluorescent emission and single-crystal X-ray diffraction. Its crystal structure is of monoclinic, space group P2 1/c with a = 9.8897（8）, b = 14.2506（12）, c = 26.384（2） ,A, β = 94.8940（10）°, V = 3704.8（5） A3 Z = 2, C86H52N16O16S2Zn4, Mr = 1891.04, Dc = 1.695 g/cm^3, μ= 1.423 mm^-1, F（000） = 1920, GOOF = 1.039, the final R = 0.0358 and wR = 0.0872 for 6038 observed reflections with I 〉 2σ（I）. In 1, ＂cage-like＂ tetranuclear clusters of [Zn4（SO4）2（DPPZ）4（HSal）2（OH）2] are further stacked through π-π interactions to generate a 3D supramolecular network.
文摘The title complex is a new binuclear Zn(Ⅱ) with chelate ligand of Schiff base containing S and N atom.The complex crystallizes in the orthorhombicspace group Pccn,with a=12.338(9),b=16.666(8),c=17.503(6),V=3599(6),Mr=723.52,Z=4,Dx=1.34 g/cm3,μ=15.22 cm-1,F(000)=1488.The structure was solved by direct methods and the final R=0.078.The crystal consists of discrete molecules with symmetric center at the center of the fourmembered ring consisting of two Zn atoms and two O atoms.
基金supported by the NNSFC (20971085)the Key Project and the Scientific Research Foundation for the Returned Overseas Chinese Scholars of State Education Ministry
文摘A homochiral complex, Zn3（Hsalen）2（Py）4（H2O）2 （salen = （1R,2R）-（-）-diamino-cyclohexane-N,N＇-biscarboxyl-salicylidene） 1, has been synthesized by solvothermal procedure and characterized by IR, microanalysis, TGA, powder and single-crystal X-ray crystallography. It crystallizes in monoclinic space group P2 with a = 10.9439（7）, b = 10.1722（6）, c = 27.3450（17）, β = 97.5060（10）o, V = 3018.1（3） 3, Z = 2, Zn3（Hsalen）2（Py）4（H2O）2, Mr = 1363.33, Dc = 1.500 g/cm3, F（000） = 1408, μ = 1.257 mm-1, GOOF = 1.042, the final R = 0.0601 and wR = 0.1464 for 10322 observed reflections with I 2σ（I）. The coordination polymer 1 possesses a 1D infinite zigzag chain architecture constructed by strong hydrogen bonding interactions and the polymeric chains are further assembled into a 2D supramolecular network structure via C–H···π interactions between the cyclohexane and aromatic rings of the ligand of adjacent chains. Simultaneously, π···π stacking interactions play an important role in forming the 2D supramolecular framework.
基金Supported by the Construct Program of the Key Discipline in Hunan Province and Key Project of Production Plan of Hengyang City(2013)
文摘A new trinuclear zinc complex Zns（2,2＂-bipy）2（3,5-DMBA）6＂（H20）1.5 （1） with 3,5-dimethylbenzoic acid （3,5-DMBA） and 2,2＂-bipyridine as ligands has been synthesized in the mixed solvents of methanol and water. It crystallizes in the monoclinic space group C2/c with a = 31.1497（15）, b = 11.7576（6）, c = 20.9049（10） A, fl = 118.4550（10）°, V- 6731.4（6） A3, Dc = 1.412 g/cm3, Z = 4, F（000） = 2972, GOOF = 1.069, the final R= 0.0667 and wR= 0.1917. The whole molecule consists of three zinc ions, six 3,5-DMBA molecules, two 2,2＂-bipyridine molecules and one and half water molecules, in which three zinc ions are bridged by six μ2-η1：η0 carboxylate groups of 3,5-DMBA. The Zn（1） atom is centrosymmetric, and adopts a distorted octahedral ZnO6 geometry, while the Zn（2） gives a distorted square pyramidal ZnOsN2 geometry. The spectroscopic characterization and thermal stability properties of the complex were investigated.
基金This work was supported by the Natural Science Foundation of Guangxi Province (No. 0229004)
文摘Two new ternary complexes [Zη（3-aba）2（phen）]·2.58H2O 1 and {[Cd（3-aba）- （phen）2]·（NO3）·（1.5H2O） }n 2 （3-aba = 3-aminobenzoic acid anion, phen = 1,10-phenanthroline） were synthesized and characterized by elemental analysis, IR, UV spectrum and X-ray diffraction. Complex 1 crystallizes in the rhombohedral system, space group R3 with a = 3.5733（3）, b = 3.5733（3）, c = 1.1231（2） nm; V= 12.419（3） nm^3, C26H25.17NaO6.58Zn, Mr= 564.37, Z= 18, F（000） = 5253, μ= 0.937 mm^-1, Dc = 1.358 g/cm^3, R = 0.0668 and wR = 0.1690 for 2424 observed reflections （I〉 2σ（I））. Complex 2 belongs to the tetragonal system, space group P4/ncc with a = 2.88451（10）, b = 2.88451（10）, c = 1.55571（11） nm, V= 12.9441（11） nm^3, C31H25CdN6O6.50, Mr = 697.97, Z = 16, F（000） = 5648,μ=0.727 mm^-1, Dc= 1.433 g/cm^3, R = 0.0607 and wR = 0.1742 for 3468 observed reflections （I 〉 2σ（I））. Complex 1 displays a mononuclear structure. The carboxylate group of 3-aminobenzoic acid anion coordinates to Zn（Ⅱ） in a chelating bidentate mode, and the nitrogen atom of the ligand does not involve in coordination. Complex 2 exhibits a one-dimensional chain structure with 3-aminobenzoic acid anion coordinating to Cd（Ⅱ） in a μ2-bridging mode through its nitrogen atom and one of its oxygen atoms.
文摘Reaction of Zn(ClO4)2·6H2O with septadentate 2,6-bis[bis(2-benzimidazolylme-thyl)amino methyl]-4-methylphenol (Hbbap) and sodium isonicotinate yielded a dinuclear zinc complex[Zn2(bbap) (Iso) (Hiso)] (ClO4)2·[Zn2 (bbap) (Iso) (H2O)] (ClO4)2·4H2O(1a·1b·4H2O). Hiso isisonicotinic acid and Iso is isonicotinate anion. The structure has been established by X-raycrystallography and shows that the two zinc ions are bridged by the phenoxy unit of bbap- ligand,and the presence of unusual monodentate O-coordination of carboxylate group from isonicotinicacid. The coordination geometry around the zinc ion is approximately trigonal bipyramidal.
基金supported by the National Natural Science Foundation of China (No. 20971004, 21171008)the Natural Science Foundation of Anhui Provincial Educational Commission (No. KJ2010A2229)the Outstanding Youth Foundation of Anhui Provincial Education Commission (No. 2010SQRL108ZD)
文摘A novel zinc（II） complex, Zn（IBT）2 （1, H1BT = 5-（4-（（1H-imidazol-1-yl）methyl）- phenyl）-2H-tetrazole） has been synthesized with Zn（NO3）2·6H2O, 4-（imidazol-l-ylmethyl）benzonnitrile （IBN） and NaN3 by the hydrothermal method, and characterized by elemental analysis, IR and single-crystal X-ray diffraction. Crystallographic data for 1： C22H18N12Zn, Mr = 515.85, orthorhombic, Pbcn, a = 16.0567（15）, b = 9.5316（9）, c = 14.6107（14） A, V= 2236.1（4） A3, Z= 4, Dc = 1.532 g/cm3,μ = 1.138 mm-1, F（000） = 1056, R = 0.0350 and wR = 0.0888 for 1438 observed reflections （I 〉 2σ（I）） and the goodness-of-fit S = 1.002 on F2. The crystal structural analysis revealed that complex 1 exhibits a rare two-dimensional homochiral wave-like layer structure. In addition, the photoluminescence of complex 1 was studied in the solid state at room temperature together with its theoretical analysis.
基金supported by the National Natural Science Foundation of China(21221001,and 21471149)Key Research Program of Frontier Science,CAS(QYZDJ-SSW-SLH028)
文摘Compounds with visible-light-induced photoluminescence are particularly attractive in acting as the emitting components of light-emitting diodes and fluorescent probes for biological applications. A new complex [Zn(NCS)_3(MQ)](MQ^+ = N-methyl-4,4?-bipyridinium) with an isolated molecular structure has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy and solid-state photoluminescent determination. Crystal data: C_(14)H_(11)N_5S_3Zn, M_r = 410.83, monoclinic, space group P2_1/c, a = 8.809(5), b = 13.138(7), c = 15.580(9) ?, b = 104.433(10)°, V = 1746.2(17) ?~3, Z = 4, D–c = 1.563 g×cm^3, μ = 1.769 mm^(–1), F(000) = 832, the final R = 0.0376 and wR = 0.1243 for 2850 observed reflections with I > 2s(I). In the crystal structure, the zinc atom is tetrahedrally coordinated by one MQ+ ligand and three NCS– groups to yield a tetrahedral configuration. The bond length of Zn–NMQ is clearly shorter than those found in reported Zn(Ⅱ) complexes of 4,4?-bipy. The isolated units are joined by C–H···S interactions to generate a 2D hydrogen-bonding network. This compound displays visible light-induced photoluminescence, which originates from both intraligand charge-transfer of the MQ+ ligand and NCS~–→MQ^+ charge-transfer according to a density of states(DOS) calculation. Moreover, its emission band shows a clear blue shift compared with those of halide compounds.
