Hydrothermal Syntheses,Crystal Structures,and Characterization of Two Zinc(Ⅱ)Complexes Containing Flexible Bis(benzimidazole)Ligands

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.

Crystal Structures of Dinuclear Copper(Ⅱ) Complexesof bis (1,4,7-triazacyclononane) Ligands Containing Rigid Bridging Groups

Dinuclear Cu(Ⅱ) complexes (Cu,LCl4). 2H2O and Cu2L'Cl4 are pre-pared and characterized by X-ray structure analysis. (Cu2I-Cl4). 2H2O, C20 H40N6Cu2Cl4O2, Mr=665. 54, monoclinic, 6 for 188l observed reflections with I>3(I). Cu2L'Cl4, C20H36N6Cu2Cl4, M.=629. 41, monoclinic, for 1330 observed reflections with I>3(I). In both complexes the stereo-chemistry about Cu(Ⅱ) is 5-coordinated with two secondary amine N atoms and twoCl- occupying sites at the base of a distorted square pyramid capped by the tertiaryamine N atom. The pair of Cl' attached to the two Cu(Ⅱ) are held in anti configuration.

Two Nickel(Ⅱ) Complexes Constructed by Novel Bis(3-methoxy-2-pyridyl)ether-6,6′-dicarboxylic Acid Ligand:Lattice Water Control of Structure

Under given conditions, two complexes of [Ni（H20）2BEDA]·2H2O 1 and [Ni（Py）2- BEDA]·6H2O 2 （BEDA = bis（3-methoxy-2-pyridyl）ether-6,6′-dicarboxylic acid） have been synthesized and characterized by elemental analysis and X-ray single-crystal diffraction. Crystal data for 1： C14H18NiN2O11, monoelinic C2/c, a = 14.3844（17）, b = 12.9900（15）, c = 9.6309（11） A, β = 104.3350（10）°, V= 1743.5（4） A3, Z = 4, Dc= 1.711 g/cm^3, F（000） = 928, μ = 1.179 mm^-1, Mr= 449.01, the final R = 0.0228 and wR = 0.0625. Crystal data for 2： C24H32NiN4O13, triclinic P1, a = 9.423（2）, b = 11.863（3）, c = 13.089（3） A, α = 91.511（3）, β = 92.465（3）, γ = 100.696（2）°, V = 1435.6（6） A^3, Z = 2, Dc= 1.488 g/cm^3, F（000） = 672, μ = 0.748 mm^-1, Mr= 643.25, the final R = 0.0400 and wR = 0.0975. Interestingly, in the two complexes, lattice water molecules dominate its crystal structures. Therefore, extensive intermolecular hydrogen bonds assemble 1 and 2 into 2D extended sheets and a 3D open framework, respectively. Furthermore, water molecules present in 2 are associated to form water clusters.

Two Three-dimensional Supramolecular Complexes Assembled by 2-Chlorinebenzoic Acid and Bis(imidazol)Ligands:Syntheses,Structures and Fluorescent Properties

Two new three-dimensional supramolecular complexes, namely, [Cd(cba)2(bib)]n(1) and [Zn(cba)2(bib)]2 n(2)(Hcba = 2-chlorinebenzoic acid, bib = 1,4-bis(imidazol-1-yl)-butane)were hydrothermally designed and synthesized. Their structures were determined by elemental analyses, IR spectroscopy, TG, fluorescence spectroscopy, single-crystal and powder X-ray diffraction. Complex 1 exhibits a one-dimensional zigzag chain and complex 2 shows a zero-dimensional structure, which were further extended into three-dimensional supramolecular structures through hydrogen bonds and π-π stacking interactions.

Weak Interactions and 2D Layer Structure of a New Ion-pair Complex Bis(1-benzyl-4-methylquinolinium)-bis(maleonitriledithiolato)nickel(Ⅱ)

A new ion-pair complex, [BzMeQ1]2[Ni（nmt）2]1（[BzMeQ1]^＋ = 1-benzyl-4-ntethylquino- linium, mnta- -- maleonitriledithiolate） has been synthesized and structurally characterized by IR, ESI-MS and X-ray diffraction methods. Complex 1 is of triclinic, space group PI, with a = 9.079（2）, b = 10.154（2）, c = 11.243（2）A, α= 81.58（1）, β= 69.63（1）, γ = 68.02（1）°, V= 940.1（3）A3, Dc = 1.427 g/cm^3, Z = 1, F（000） = 418 and R = 0.0442. A 2D layer structure is formed via the cation-cation π…π and C-H…π interactions observed in the solid state of the complex.

POLYMERIZATION OF ETHYLENE WITH UNSYMMETRIC 2,6-BIS(IMINO)PYRIDINE IRON(Ⅱ)COMPLEX

An unsymmetric 2,6-bis(imino)pyridine iron(II) complex 1' was synthesized. The relationship between catalyststructure and its activity in ethylene polymerization is discussed. The kinetic behavior of ethylene polymerization and theeffects of polymerization conditions such as temperature, aluminum/iron molar ratio on the activity of catalyst and thecharacteristics of polyethylene were reported. The unsymmetric catalyst 1' has a good catalytic performance of 3.47×10~6 gPE·mol^(-1)·Fe·h^(-1) at 40℃ with aluminum/iron molar ratio = 2500. A dependence of catalyst activity on themethylaluminoxane (MAO) concentration and reaction temperature was found. The molecular weight (MW) of polyethylenewith broad dispersity is about 10~4-10~5 g/mol. The melting temperature and branching of polyethylenes vary with changingreaction temperature and aluminum/iron molar ratio.

Characterization and Crystal Structures of Two Copper(Ⅱ) Complexes Constructed by a Flexible Double Betaine Ligand

A flexible double betaine 1,4-bis（pyridinil-4-carboxylato）-1,4-dimethylbenzene L has been used to generate two Cu（Ⅱ）-containing metal complexes that exhibit different polymeric structures： [Cu（H2O）2 L].2NO3 1 and [Cu（H2O）3 L].2Cl.H2O 2. The crystal structures of 1 and 2 have been determined by single-crystal X-ray diffraction method. Crystal data for 1： triclinic, space group PT, a = 5.253（2）, b = 7.406（3）, c = 14.792（5） A, α = 84.195（5）, β = 80.014（5）, γ = 78.053（5）°, V= 553.2（3）A^3, Z = 1, F（000） = 293, Dc = 1.717 g/cm^3, the final R = 0.0385 and wR = 0.1079 for 1883 observed reflections （I 〉 2σ（I））; and those for 2： monoclinic, space group P21/c, a = 10.222（3）, b = 25.287（7）, c = 9.277（3）A, β = 93.572（5）°, V = 2393.2（12）A^3, Z = 4, F（000） = 1140, Dc = 1.540 g/cm^3, the final R = 0.0472 and wR = 0.0956 for 3204 observed reflections （I 〉2o（/））.

Synthesis,Crystal Structure and Theoretical Calculations of a Cadmium Complex Containing 3-Hydroxybenzoic Acid and 1,4-Bis(imidazol-1-yl)-butane

A new complex [Cd（hba）2（bib）]n·nH2O（1,Hhba = 3-hydroxybenzoic acid,bib = 1,4-bis（imidazol-1-yl）-butane） has been hydrothermally synthesized and characterized by elemental analysis,IR spectrum,thermogravimetric analysis,fluorescence spectrum,and singlecrystal X-ray diffraction.Yellow crystal crystallizes in the orthorhombic system,space group Pbca with a = 16.220（5）,b = 14.980（5）,c = 20.521（5） ？,V = 4986（3） ？~3,C（24）H（26）CdN4O7,Mr = 594.89,Dc = 1.585 g/cm^3,μ（Mo Kα） = 0.927 mm^（-1）,F（000） = 2416,Z = 8,the final R = 0.0242 and w R = 0.0589 for 4076 observed reflections（I 〉 2s（I））.In 1,the Cd（Ⅱ） ion takes a six-coordination mode,and bib ligand bridges adjacent Cd（Ⅱ） ions to generate 1D zigzag chains; these neighboring chains are connected by O–H···O hydrogen bonding interactions,producing a 2D folded layered structure.Furthermore,by O–H···O hydrogen bonding between layers and layers,a 3D supramolecular architecture is formed.In addition,we analyzed Natural Bond Orbital（NBO） in using the PBE0/LANL2 DZ method built in Gaussian 03 Program.The calculation results indicated obvious covalent interaction between the coordinated atoms and Cd（Ⅱ） ion.

Synthesis and Crystal Structure of cis-[meso-1, 3-Bis(propylsulfinyl)propane]dichloroplatinum(Ⅱ)

A mononuclear complex, cis-[meso-1, 3-bis(propylsulfinyl)propane]- dichloroplatinum(Ⅱ) (Pt(C9H20O2S2)Cl2) 1, has been prepared and structurally characterizated by single-crystal X-ray diffraction. The crystal belongs to orthorhombic system, space group Pna21 with a = 22.800(3), b = 11.7662(13), c = 5.8115(6) ? V = 1559.0(3) ?, Mr = 490.36, Dc = 2.089 g/cm3, Z = 4, F(000) = 936, m (MoKa) = 9.596 mm-1 and l = 0.71073 ? The structure was refined to R = 0.0204 and wR = 0.0473 for 2703 reflections with I > 2(I). It is revealed that the central Pt(Ⅱ) ion in the title complex is bonded to two Cl atoms in a cis-configuration and two S atoms of the ligand to form the coordination geometry deviating slightly from the square planar.

Hydrothermal Synthesis, Crystal Structure and Surface Photo-electric Properties of a New Nickel(Ⅱ) 3-D Metalorganic Framework Constructed from the Rigid 1,4-Bis(imidazol-1-yl) benzene Ligand

A new 3-D nickel（Ⅱ） metal-organic framework（MOFs） with formula [Ni（bib）_2（SO_4）]_n（1）, where bib = 1,4-bis（imidazol-1-yl）benzene, has been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and surface photovoltage spectroscopy（SPS）. Complex 1 crystallizes in monoclinic system, space group C2/c with a = 19.5988（6）, b = 9.7531（3）, c = 11.8146（4） ？, β = 96.185（3）°, V = 2245.20（12） ？~3, C_（24）H_（20）N_8NiO_4S, M_r = 575.25, D_c = 1.702 g/cm^3, Z = 4, F（000） = 1184, μ = 1.011 mm-1, the final R = 0.0293 and w R = 0.0702. X-ray diffraction analyses indicated that the center Ni^（2＋） ion is six-coordinated with an O_2N_4 donor set of two μ_2-SO_4^（2–） and four bib ligands, resulting in an ideal octahedral geometry. Topological analysis on complex 1 considers each Ni^（2＋） as a 6-connected node, while bib and sulfate ion as linkers, giving an α-Po topology with short Schl？fli symbol 412·63. In the crystal packing, the components interact with pairs of intermolecular C–H×××O hydrogen bonds. The SPS of 1 indicates that there are positive response bands in the range of 300~600 nm showing photo-electric conversion properties.

Ni(Ⅱ)与Hbbimp配合物的合成、表征及晶体结构

A new complex with binuclear nickel(Ⅱ) complex [Ni2(bbimp)(CH3CH2OH)2Cl2]Cl· 4H2O (bbimp=2,6 bis[bis(2 benzimidazolylmethyl)]aminomethyl 4 methylpheno)(o)had been synthesized and characterized by elementary analysis, IR and UV. The molecular structure of the title complex was determined by X ray single crystal diffraction method. The crystal is monoclinic, space group P21/n with a=20.803(2)? , b=30.708(3)? , c=20.959(2)? , β =105.776(2)° , Z=8, V=12885(2)? 3, Dx=1.132Mg· m- 3, μ =0.755mm- 1, F(000)=4592, R1=0.1267, S=1.376. It was showed that the nickel? cation is the central ion of a distorted octahedral coordination with two N belonging to benzimidazole, a bridging phenolate O, a N of tertiary amine, a Cl anion, and an O of an ethanol molecule. Two nickel? cations in a molecular structure had the same coordinated environment. CCDC: 197601.

Syntheses, Structures and Characteristics of Two New Cu(II) Coordination Polymers Based on 4-tert-butyl-phthalate and Different Bis(1,2,4-triazol-1-yl) Co-Ligands

Two new Cu（Ⅱ） coordination polymers, [Cu2（tbph）2（btb）2]n （1） and {[Cu2（tbph）2- （bth）2]·H2O}n （2）, （H2tbph = 4-tert-butyl-phthalic acid, btb = 1,4-bis（1,2,4-triazol-1- yl）butane, bth = 1,6-bis（1,2,4-triazol-l-yl）hexane）, have been synthesized and characterized by elemental analysis, FT-IR and X-ray single-crystal diffraction. Complex 1 has a 2D sql layer. Complex 2 shows a （3,4）-connected 2D sheet with a （4.6^4.8）（4.8^2） topology. The thermal behavior of the two cor- responding complexes has briefly been investigated.

One-dimensional Zigzag Chain Composed of HgI_2 Unit and 2,5-Bis(4-pyridyl)-1,3,4-thiadiazole:[HgI_2(C_(12)H_8N_4S)]

The title compound, [HgI2（C12H8N4S）], has been synthesized and characterized by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/n with a = 14.086（2）, b = 6.0365（6）, c = 20.286（2）°A,β= 108.818（5）°, V = 1632.7（3）°A^3, Mr = 694.67, Z = 4, D, = 2.826 g/cm^3,μ= 13.331 mm^-1, F（000） = 1240, S = 1.108, the final R = 0.0438 and wR = 0.0934 for 3085 observed reflections （I〉 2σ（I））. The Hg（Ⅱ） atom is coordinated by two 2,5-bis（4-pyridyl）-1,3,4-thiadiazole （L） molecules and two iodine anions in a distorted tetrahedral coordination geometry. Mercury atoms are linked by the organic ligands to form a one-dimensional zigzag chain. It is noteworthy that such 1D zigzag chains are extended into a two-dimensional double layer framework through I…I interactions

SYNTHESIS AND CHARACTERIZATION OF THE SOLID COMPLEXES OF Eu (Ⅱ,Ⅲ)WITH OCTANEDIOYL-BIS(BENZO-15-c-5)

The study of rare earth complexes with crown ether arouses people’s great interest. The previous research work was focused on the complexes with single crown ether. Because of the coordinated actions with metal ions of the two crown ether cycle activities, the bis (crown ether)has better coordination and selectivity than the single crown ether ligands.

二(芳氧基)稀土(Ⅱ)配合物催化ε-己内酯开环聚合

系统地研究了二（２，６二叔丁基４甲基酚基）钐［（ＡｒＯ）２Ｓｍ（ＴＨＦ）４］催化ε己内酯的开环聚合，发现它具有很高的催化活性并显示“活性”聚合的特点，在甲苯中，当［Ｍ］／［Ｉ］＝２０００（摩尔比），６０℃，１ｈ，转化率可达９８％．并比较了不同的两价稀土化合物的催化活性．通过核磁分析末端基结构的方法，研究了（ＡｒＯ）２Ｓｍ催化己内酯开环聚合的引发机理，发现催化剂首先与己内酯反应，生成三价烯醇式稀土化合物，后者引发己内酯聚合．

双Salamo型四肟配体构筑的锌(Ⅱ)配合物：合成,晶体结构和荧光性质(英文)

通过二水乙酸锌(Ⅱ)和双Salamo型四肟配体6,6′-二乙氧基-双(2,2′-(乙二氧双(氮次甲基)))四酚(H4L)的配位反应,合成了2种锌(Ⅱ)配合物即:[Zn_3(L)(OAc)2(H_2O)](1)和[Zn3(L)(OAc)2(H2O)]·[Zn3(L)(OAc)2(CH_3OH)(H_2O)]·3CH_3OH·H_2O(2)。该类配合物含有2个Salamo型L4-配体和3个锌(Ⅱ)离子,其中2个锌(Ⅱ)原子位于Salamo型螯合单元的N2O2空腔内。[Zn(L)]螯合物中桥联的酚氧原子进一步和中心的锌(Ⅱ)原子配位。这类结构能通过2个桥联的乙酸根配体稳定,从而使配合物1和2达到电荷平衡。配合物有2种不同的几何构型即扭曲的三角双锥和四方锥(配合物1)或三角双锥和八面体(配合物2)。另外,配合物1和2在激发波长为340和337 nm时能发出强的绿光,其最大发射波长分别为531和536 nm。

三(2-苯并咪唑亚甲基)胺铜(Ⅱ)配合物的合成、晶体结构和量子化学研究

合成了高氯酸［ 三（２苯并咪唑亚甲基） 胺］ 咪唑合铜（ Ⅱ） 配合物［ Ｃｕ（ Ｃ２７ Ｈ２５ Ｎ９）］（ Ｃｌ Ｏ４）２ ·２ Ｃ Ｈ３ Ｏ Ｈ· Ｈ２ Ｏ。用 Ｘ射线衍射的方法测定了其晶体结构，并对其混合配体进行了量化计算。配合物晶体结构属三斜晶系，空间群为 Ｐ１－ ，晶胞参数：ａ ＝ １１ ．３７７（４） ， ｂ ＝ １２ ．３８０（２） ， ｃ＝ １５ ．０６８（５） 〓，α＝ ６６ ．１６（２）°， β＝ ７２ ．４１（３）°， γ＝ ７４ ．００（２）°， Ｖ＝ １８２１ ．５ 〓３ ， Ｚ＝ ２ ， Ｆ（０００） ＝ ７２６ ， Ｄｃ ＝ １ ．４９１ ｇ／ｃｍ３ ， Ｍｒ＝ ８１８ ．０９ ， μ（ Ｍｏ Ｋα） ＝ ８ ．１３３ ｃｍ － １ 。结构由重原子法和傅里叶合成法解出，利用全矩阵最小二乘法进行修正，最终偏离因子 Ｒ＝ ０ ．０７ ， Ｒｗ ＝ ０ ．０９ 。 Ｃｕ２ ＋ 与混合配体的五个 Ｎ 原子配位形成扭曲的三角双锥构型。量子化学计算表明 Ｃｕ２ ＋ 处于由五个 Ｎ 原子包围的大小适宜的负电荷的空穴内。

双穴二氧四胺Cu（Ⅱ）和Ni（Ⅱ）配合物的合成和性质

本文合成了二种新配体，Ｎ，Ｎ＇－双［水杨醛缩（２－氨乙基）］乙二酰胺（ｄｓａｅ）和Ｎ，Ｎ＇－双［水杨醛缩（２－氨乙基）］丙二酰胺（ｄｓａｐ）及其Ｃｕ、Ｎｉ的配合物，并用元素分析、红外、摩尔电导、磁化率表征，测定了ＣｕＨ－２ｄｓａｐ配合物的稳定常数，结果表明Ｃｕ、Ｎｉ与ｄｓａｅ生成双核配合物，Ｃｕ与ｄｓａｐ生成单核配合物，并对其原因进行了讨论．

吡啶双亚胺酰氯Ni(Ⅱ)配合物的合成、表征及催化合成液体聚丁二烯

合成了一系列吡啶双亚胺酰氯三齿Ni(Ⅱ)配合物(1a^1c,2a^2c),通过傅里叶变换红外光谱和元素分析对配合物进行表征,测定了配合物1a^1c的晶体结构.3个化合物同属于单斜晶系,且都具有以Ni原子为中心的近似于C s对称的扭曲三角双锥构型.该系列配合物通过倍半乙基氯化铝(EASC)活化,在20℃下对丁二烯聚合表现出良好的催化活性,得到分子量为4700~5200、cis-1,4含量为74.8%~77.2%(摩尔分数)的液体聚丁二烯.通过改变配体的结构和聚合条件,可在一定范围内调控聚丁二烯的结构和分子量.

配体结构对钌(Ⅱ)联吡啶配合物的电子结构的影响

本文用ＣＮＤＯ／２方法计算获得了钌（Ⅱ）联吡啶配合物［Ｒｕ（ｂｐｙ）２（ＬＬ）］２＋的电子结构参数（其中ＬＬ为二齿螯合配体，２－（３－硝基苯基）吡啶阴离子，３－甲基－５－（２′－吡啶基）－１，２，４－三唑阴离子，５，５′－二甲基－２，２′－二－１，３，４－硫代吡咯，２，３－二（２－吡啶基）喹喔啉，邻苯醌二亚胺，邻苯醌。讨论了配体ＬＬ的结构对该系列配合物的电子结构、光谱和电化学性能的影响。计算结果与实验结果相吻合，体现的规律性也是一致的。