Hydrothermal Synthesis, Crystal Structure and Luminescence Properties of a New 2D Cadmium Complex Based on the 4,4'-Bis(benzimidazol-1-ylmethy1)biphenyl and Glutaric Acid Ligands

A new polymeric complex {[Cd2（bbmb）2（gt）2]＇（H2O）2}, （bbmb = 4,4＇-bis（benzimidazol-l-ylmethyl）biphenyl, H2gt = glutaric acid） has been obtained by hyclrothermal method and structurally characterized by elemental analysis, IR, XRD, TGA and single-crystal X-ray diffraction. The complex belongs to the triclinic system, space group P1 with a = 10.2417（15）, b = 13.752（2）, c = 22.201（3） A, a = 73.899（2）, β = 88.416（2）, y = 78.305（2）°, V = 2940.4（7） A3, Z = 2, C66H56Cd2N808, Mr = 1313.99, Dc = 1.484 g/cm3, F（000） = 1336 and μ = 0.787 mm-1, and features a 2D network. In the solid state at room temperature, the cadmium（Ⅱ） complex exhibits strong fluorescence absorption at 435 nm （λmax）.

Synthesis, Crystal Structure and Luminescent Property of a Dinuclear Cadmium Complex Based on 1,2,3,4-Tetra(1H-benzo[d]imidazol-2-yl)butane

A complex [Cd2（tbb）C14]·4DMF·3H2O, where tbb is 1,2,3,4-tetra（1H-benzo[d]imi- dazol-2-yl）butane, was synthesized and characterized by X-ray single-crystal structure analyses. For this complex： C44H49Cd2C14N12OT, Mr= 1224.55, monoclinie system, space group C2/c, a = 29.563（3）, b = 14.2580（17）, c = 26.355（3） A,β = 97.036（2）°, V = 11025（2） A3, Z = 8, D,.= 1.475 g/cm3, 2 = 0.71073 A, IL（MoKa） = 1.021 mm-1, F（000） = 4936, S = 1.047, R = 0.0680 and wR = 0.1832 for 11812 observed reflections with I 〉 2σ（I）. It is a neutral dinuclear complex. One 1,2,3,4-tetra（1H-benzo[d]imidazol-2-yl）butane coordinates to two cadmium ions. Each cadmium ion is coordinated by two nitrogen atoms of tbb and two chloride ions. The complex emits blue luminescence in DMF solution as well as in solid powder state.

Synthesis, Crystal Structure and Luminescent Property of a Dinuclear Cadmium Complex Based on 1,2-Bis(1-phenyl-1H-benzo[d]imidazol-2-yl)benzene

A dinuclear cadmium complex [Cd2（bpbb）2Cl2（μ-Cl2）], where bpbb is 1,2-bis（1-phenyl-1H-benzo[d]imidazol-2-yl）benzene, was synthesized and characterized by X-ray singlecrystal structure analyses. Crystal data： C（64）H（44）Cd2Cl4N8, Mr = 1291.67, triclinic system, space group P1, a = 10.076（3）, b = 12.730（4）, c = 13.176（4） A, α = 99.087（3）, β = 109.859（3）, γ = 112.551（3）°, V = 1384.8（7） A3, Z = 1, Dc = 1.549 g/cm^3, λ = 0.71073 A, μ（Mo Kα） = 1.010 mm^（–1）, F（000） = 648, S = 1.062, R = 0.0425 and wR = 0.1130 for 9688 observed reflections with I 〉 2s（I）. One 1,2-bis（1-phenyl-1H-benzo[d]imidazol-2-yl）benzene coordinates to one cadmium ion. The cadmium is five-coordinated by three chloride ions and two nitrogen atoms from bpbb. Each cadmium ion is bridged by two chloride ions. The decomposition temperature is up to 420 ℃. The complex emits blue luminescence in DMF solution and in solid powder state.

Synthesis, Crystal Structure and Luminescence Property of a Cd(Ⅱ) Complex Assembled by 4-Carboxymethoxy Phenylacetic Acid

A new structure with the molecular formula [CdL]n was formed by CdSO4 with 4-carboxymethoxy phenylacetic acid （H2L） through the hydrothermal method. The complex was characterized by elemental analysis and infrared spectroscopy. The structure of the complex was determined by single-crystal X-ray diffraction, which is of monoclinic system, space group P21/c with a = 10.3887（2）, b = 7.10710（10）, c = 14.7212（2） , β = 120.6940（10）°, V = 934.65（3） 3, Dc = 2.278 g·cm-3, Z = 4, F（000） = 624, S = 1.022, the final R = 0.0187 and wR = 0.0487 for 2000 observer reflections （Ⅰ 〉 2σ（Ⅰ））. The center metal ion Cd（Ⅱ） in the complex is six-coordinated in a distorted octahedral geometry, and is connected with L ligands to form a 3D fishing net structure, which is a novel （3,6） network topology. The luminescence of the complex has been investigated, and the result reveals that it displays luminescent property in the voilet region.

Synthesis, Crystal Structure and Luminescent Property of a Dinuclear Cadmium Complex Based on 2-(2-(1H-Benzo[d]imidazol-2-yl)-phenyl)-1-phenyl-1H-benzo[d]imidazole

A dinuclear cadmium complex [Cd_2（bppb）Cl_4×2DMF]（1）, where bppb is 2-（2-（1 Hbenzo[d]imidazol-2-yl）phenyl）-1-phenyl-~1 H-benzo[d]imidazole, was synthesized and characterized by X-ray single-crystal structure analyses. For 1： C_（58） H_（50） Cd_2 Cl_4 N_（10） O_2, M_r = 1285.68, monoclinic system, space group P2_1/n, a = 16.136（3）, b = 10.612（2）, c = 16.270（3） ？, β = 96.209（2）°, V = 2769.7（9） ？~3, Z = 2, D_c = 1.542 g/cm^3, λ = 0.71073 ？, μ（Mo Kα） = 1.013 mm^（–1）, F（000） = 1296, S = 1.055, R = 0.0393 and wR = 0.1185 for 4876 observed reflections with I 〉 2σ（I）. One 9 mium ion which is five-coordinated by three chloride ions and two nitrogen atoms from bppb. Two cadmium ions are bridged by two chloride ions. The Cd_2（bppb）_2 Cl_2（μ-Cl_2） decomposes at 350 ℃ which is much lower by 70 ℃ than [Cd_2（bpbb）_2 Cl_2（μ-Cl_2）]（420 ℃）. The complex emits blue luminescence in both DMF solution and solid powder. Phenyl ring substituting NH hydrogen atom of benzimidazole group in ligand can not obviously change the UV-vis and luminescence spectra peaks location of the benzimidazole cadmium complex.

Crystal Structure and Photoluminescence of a New Cadmium Complex with 6,7-Dicyanodipyridoquinoxalin

The reaction of CdCl2 with 6,7-dicyanodipyridoquinoxaline （DICNQ） by solvothermal reaction gives rise to a coordination polymer [CdCl2（DICNQ）]n 1. Single-crystal X-ray diffraction analysis reveals that the compound in space group Pbcn creates 1-D chloro-bridging chains. Crystal data for 1： a = 6.756（1）, b = 35.371（6）, c = 7.027（1）A , V = 1679.1（5） A^3, Z = 4.00, C16H6CdCl2N6, Mr = 465.57, Dc = 1.842 g/cm^3, μ = 1.630 mm-1, F（000） = 904, S = 1.005 and T = 293（2） K. The final R = 0.0376 and wR = 0.1029 for 1291 observed reflections with I 〉 2σ（I）, and R = 0.0499 and wR = 0.1125 for all data. The 1-D chloro-bridging chains are parallel-stacked in the a and b directions, and further stabilized through π-stacking interactions, hydrogen-bonding interactions and C≡N···π interactions to generate a 3-D structure. Compound 1 displays intense bluish-green photoluminescence from the intraligand charge-transfer of the DICNQ ligand and the Cl--to-DICNQ charge-transfer mechanism which is probed by the density of states （DOS） calculations.

Synthesis,Crystal Structure and Luminescent Property of Cadmium Complex Based on 2-(2-(1Hbenzo[d]imidazol-2-yl)benzyl)-1H-benzo[d]-imidazole

The complex [Cd（bbb）Cl2]·DMF·H2O, where bbb is 2-（2-（1H-benzo[d]imidazol-2-yl）benzyl）-1H-benzo[d]imidazole, was synthesized and characterized by X-ray single-crystal structure analyses. For the complex： C24H25Cl2CdN5O2, Mr = 598.77, crystal system, triclinic, space group P1, a = 9.9878（12）, b = 10.0008（12）, c = 13.2217（15） , α = 80.674（2）, β = 72.158（2）, γ = 86.776（2）°, V = 1240.5（3） 3, Z = 2, Dc = 1.598 g/cm3, λ = 0.71073, μ（MoKα） = 1.127 mm–1, F（000） = 600, S = 1.04, R = 0.0905 and wR = 0.3088 for 4805 observed reflections with I 〉 2σ（I）. It is a neutral complex. The distorted tetrahedral geometry of cadmium ion is coordinated by two nitrogen atoms of ligand and two chloride ions. The complex emits blue green luminescence with emission peaks at 480 nm in DMF solution.

Cadmium(II)-1,4-phenylenediacetate Complex with Green Luminescence

The title complex, formulated as {[Cd（pda）（phen）]·3H2O}, 1 （pda = 1,4-phenylenediacetate, phen = 1,10′-phenanthroline）, has been hydrothermally synthesized and determimned by X-ray crystallography. Crystallographic data： triclinic, space group P1^-, a = 10.375 （7）, b = 10.435（1）, c = 12.040（1） A.α = 68.503（1）, ,β= 86.371（1）, γ= 66.231（1）°, Mr = 538.82, V = 1104.5（8） ,A^3, Z = 2, Dc = 1.620 g/cm^3,μ = 1.035 mm^-1, F（000） = 544, the final R = 0.0380 and wR = 0.0985 （w = 1/[σ^2（F0^2） ＋ （0.0559P）^2 ＋ 1.5319P], where P = （F0^2＋ 2Fc^2）/3） based on 3444 observed reflections with I 〉2σ（I）. Complex 1 features a two-dimensional layer. Fluorescent analysis reveals that it exhibits intense green luminescence with the maximum at around 516 nm.

Synthesis and Crystal Structure of 1D Chloride Bridged Cadmium(Ⅱ) Chain

Hydrothermal reaction of 1,10-phenanthroline with CdCl2·2.5H2O in aqueous solution leads to the complex of [Cd(μ-Cl)2(phen)]n (phen = 1-10-phenanthroline). The crystal structure has been determined by X-ray analysis. It crystallizes in monoclinic with space group C2/c, a = 16.947(3), b = 10.529(2), c = 7.235(1) , β = 110.795(3)°, V = 1208.8(3) 3, Z = 4, Dc = 1.997 g.cm-3, μ= 2.22 mm-1, F(000) = 704, R = 0.0231, Rw = 0.0626 for 1194 reflections with I > 2σ (I). In the crystal structure, the [Cd(phen)]2+ units are bridged by chloride ions to form 1D chain. The 1D chains combine through π……π interactions of phen groups to form 2D infinite molecular zipper.

A Silver Complex of 6,7-Dicyanodipyridoquinoxaline:π-Stacking Interactions and Luminescence

The reaction of 6,7-dicyanodipyridoquinoxaline （DICNQ） with AgNO3 in a 1：1 molar ratio by solution method gave a new complex [Ag（DICNQ）2]NO3 1. Single-crystal X-ray diffraction analysis reveals that the complex crystallizes in the space group Ibca of orthorhombic system with eight formula units in a cell. Crystal data for 1： a = 15.7055（17）, b = 18.411（2）, c = 20.680（2）A, V = 5979.7（11）A3, Z = 8, C32Hl2AgN13O3, Mr = 734.42, Dc = 1.632 g/cm3, μ= 0.734 mm-1, F（000） = 2928, S = 1.023 and T= 293（2） K. The final R = 0.0659 and wR = 0.1927 for 2118 observed reflections with I 〉 2σ（I）, and R = 0.0801 and wR = 0.2196 for all data. The complex builds up a packing structure by π-π stacking interactions and shows a luminescent feature.

Synthesis, Crystal Structure and Luminescent Property of [Zn(C_(12)H_9O_3)_2(C_(10)H_8N_2)]_n·nH_2O

Under hydrothermal condition, the reaction of 2-naphthoxyacetic acid with ZnCl2 and 4,4′-bipyridine （4,4′-bipy） has afforded a new Zn（Ⅱ） compound, [Zn（C12H9O3）2（C10H8N2）]n·nH2O1, which was structurally characterized by single-crystal X-ray diffraction analysis. The crystal is of monoclinic, space group P21/c with a = 7.7335（2）, b = 19.3834（4）, c = 20.1707（4） A, β = 104.9830（10）°, V = 2920.82（11） A^3, C34H28ZnN2O7, Mr = 641.95, Z = 4, Dc = 1.460 g/cm^3,μ = 0.895 mm^-1, F（000） = 1328, R = 0.0406 and wR = 0.0876 for 4417 observed reflections （I〉 2σ（I）） Complex 1 consists of one-dimensional zigzag chains deriving from Zn（C12H9O3）2 units linked by 4,4′-bipy ligands, and lattice water molecules decorate between the chains. Non-covalent interactions, such as hydrogen-bonding and aromatic π-π interactions, lead to the formation of a 3D network structure. The thermogravimetric analysis （TGA） and luminescent property for 1 have also been studied in this paper.

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 Structure of a Novel Macrocyclic Complex [Cd_2(phen)_4(phth)_2]·4H_2O

A novel complex [Cd2（phen）4（phth）2]·4H2O has been synthesized by the reaction of Hzphth（phthalic acid） and phen（1,10-phenanthroline） with Cd（Ⅱ） in ethanol-water solution. X-ray crystal structure analysis shows it crystallizes in triclinic, space group PI- with a = 10.619（3）, b = 12.560（4）, c = 12.651（4） A, a = 98.775（5）, β = 109.035（5）,γ = 113-576（5）°, C32H24CdN4O6, Mr= 672.95, V = 1381.7（7）A^3, Rint = 0.0358, Z = 2, Dc= 1.618 g/cm^3,μ = 0.845 mm^-1, -6 ≤h≤13, -15 ≤k ≤13, -15 ≤l≤14, F（000） = 680, S = 1.038, R = 0.0480 and wR = 0.0849 for 3992 observed reflections （1 〉 2σ（Ⅰ））. Phth bridges Cd（Ⅱ） to form a macrocyclic compound, and a 2D supramolecular motif is formed through hydrogen bonds and π-π interaction.

Synthesis,Characterization and Antitumor Activity in Vitro of Cd(Ⅲ)Complex with Chelidamic Acid

A novel complex [Cd4（HCAM）4（H2O）8] of Cd（Ⅲ） withchelidamic acid （H3CAM） was synthesized by the hydrothermal method and characterized with IR and emission spectra.The crystal structure was determined based on single-crystal X-ray diffraction data.It crystallizes in monoclinic,space group C2/c with a=17.538（5）,b=12.916（4）,c=16.505（7）,β=100.690（14）o,V=3674（2） 3,Z=8,C14 H14 Cd2N2O14,Mr=659.07,Dc=2.383 g/cm 3,μ=2.400 mm-1,S=1.000,F（000）=2560,the final R=0.0242 and wR=0.0581 for 3656 observed reflections with I〉2σ（I）.The inhibition of the complex against K562 and HL60 cells was determined by MTT assay.The results showed that the concentration of complex was positively correlated with inhibitions against K562 and HL60 cell lines,but inhibitory effects are relatively weak.IC 50 concentration of the title complex on K562 and HL60 cells is 15 and 5 μg/mL,respectively.

A series of 3D lanthanide complexes based on H bond and halogen-halogen interactions：Synthesis, structure, spectroscopic and thermal properties

Four lanthanide coordination complexes, namely, [Ln（2,3-DClBA）3（5,5’-dmebipy）（H2O）]2（Ln=Sm（1）, Eu（2）, Dy（3）, Ho（4））; 2,3-DClBA=2,3-dichlorobenzoate; 5,5’-dmebipy=5,5’-dmethylbipyridine） were synthesized and characterized by elemental analysis, infrared spectroscopy and single crystal X-ray diffraction. Findings indicated that complex 3 was a dinuclear molecule, and the center Dy3＋ was eight-coordinated. Each dinuclear units could be connected by H bond and halogen-halogen interactions. Luminescent property of complex 2 suggested the typical intense emissions of Eu3＋ ions. Thermal analysis showed that the complexes decomposed in three steps： the coordination water was lost firstly then the neutral ligand 5,5’dmebipy was lost and lastly the 2,3-DClBA ligand was lost.

三维网状配位聚合物｛[Cd2(phen)2(H2O)2(C6H5NO2)2]·(ClO4)｝n的水热合成、晶体结构及荧光性质

以异烟酸和邻菲咯啉(phen)为原料,采用水热合成方法,合成了一个新的配位聚合物{[Cd2(phen)2(H2O)2(C6H5NO2)2].(ClO4)}n,测定了其晶体结构。结果表明:该配合物晶体属单斜晶系,空间群P21/n。与中心镉!离子配位的3个氧原子分别来自2个异烟酸根和1个水分子,3个氮原子分别来自1个异烟酸根和1个邻菲咯啉,形成六配位变形八面体结构。由于异烟酸的桥联作用及氢键作用,配合物堆积成三维网状结构;同时配合物通过异烟酸的羧基双齿桥联配位以及邻菲咯啉和水分子作为端基配位,形成了双核笼状结构,其Cd!…Cd!距离为0.8798 nm。此外,还研究了该聚合物的荧光性质。

一维Z型链状配合物[Cd(BDC)(H_2C2EIm)(H_2O)]_n的水热合成、晶体结构和荧光性质研究(英文)

水热合成了1个新配合物[Cd(BDC)(H2C2EIm)(H2O)]n(BDC=对二苯甲酸;H2C2EIm=2,2′-乙基双苯丙咪唑)。通过元素分析、红外光谱、热重以及X-射线单晶洐射对其进行了表征。该晶体属三斜晶系,P1空间群。Cd髤原子通过BDC和H2C2EIm 2种配体连接成一维Z型带状结构,带与带之间通过N-H…O,O-H…O连接成三维超分子结构。室温下配合物具有较强的荧光发射光谱。

二聚体配合物[Cd(5-oxo-4-oxa-tricyclo[4．2．1．0]nonane-9-carboxylic radical)2(phen)]2的合成、晶体结构及荧光性质

由简单小分子配体和金属镉离子形成的配合物通过氢键可以构筑具有高级有序结构的分子聚集体，这些分子聚集体在制备具有磁性、生物活性、光学性质和催化性能等新材料方面有着潜在的应用前景。由于Cd（Ⅱ）金属配合物具有很好的荧光性能及抗菌等性质而受到人们关注。近年来．对于以羧酸为配体与金属离子配位形成的配合物有大量报道．

含dmpzm配体的锌和镉配合物的合成、结构及性质研究

通过M(NO3)2(M=Zn,Cd)和二(3,5-二甲基吡唑)甲烷(dmpzm)的反应,合成了2个锌和镉配合物[M(dmpzm)2(NO3)][NO3](1:M=Zn;2:M=Cd)。配合物1和2经元素分析,红外光谱表征,并经X射线单晶衍射法证实。配合物1属于正交晶系,空间群为Pca21,晶体学参数:a=1.6259(3)nm,b=0.83210(17)nm,c=2.0311(4)nm,V=2.7479(10)nm3,Z=4。配合物2属于正交晶系,空间群为Pca21,晶体学参数:a=1.67436(15)nm,b=0.82129(7)nm,c=2.04801(19)nm,V=2.8163(4)nm3,Z=4。在这2个配合物的阳离子中,金属原子分别与2个dmpzm中的4个N原子及1个NO3-中的2个O原子配位,形成略为畸变的八面体构型。配合物1和2的晶体中,NO3-的O原子与配体dmpzm中的甲基及亚甲基间存在的C-H…O氢键作用,从而形成了有趣的三维网状结构。此外,还研究了配合物1和2的荧光性质。

一维链状配位聚合物[Cd(phen)(α-Furacrylic radical)2]n的水热合成、晶体结构及荧光分析

羧酸配合物具有丰富的拓扑结构。在磁学、光学、催化、生物等诸多领域有广泛的应用前景，人们对羧酸配合物的研究一直保持着浓厚的兴趣。近年来，我们也合成了一些新的羧酸配位聚合物，并对其性质进行了分析．我们使用较多的配体主要是芳香羧酸、柔性羧酸及杂环饱和羧酸，而以杂环不饱和羧酸和邻菲咯啉为配体的镉配位聚合物报道相对较少。