A New Manganese(Ⅱ) Coordination Compound Constructed by 1,10-Phenanthroline Derivative and Chlorine Anions: Synthesis, Crystal Structure and Theoretical Calculation

The new manganese（Ⅱ） coordination compound, [Mn（Cl）2（L）2]（1, L = 11-fluorodipyrido[3,2-a:2?,3?-c]phenazine）, has been achieved under hydrothermal conditions. The structure of compound 1 was determined by single-crystal X-ray diffraction. 1 crystallizes in monoclinic system, space group C2/c with a = 8.419（2）, b = 12.286（2）, c = 28.451（6） ?, β = 95.889（3）°, V =2927.5（10） ?3, Z = 4, C36 H16 MnF2 Cl2 N8, Mr = 724.41, Dc = 1.644 g/cm3, F（000） = 1460, μ（Mo Ka）= 0.691 mm-1, R = 0.0445 and wR = 0.0982. Adjacent compounds are stacked by one type of π-πinteraction among L ligands to generate a 1D supramolecular chain. Further, the 1D supramolecular chains are stacked by another type of π-π interaction among L ligands to give a 2D supramolecular layer. Moreover, the C-F···π interactions between the carbon atom of the L ligand and the pyrazine ring of the adjacent L ligand further stabilize the supramolecular layer of 1. In addition, natural bond orbital（NBO） analysis has been calculated by the B3LYP/LANL2DZ method, which shows obvious covalent interaction between the coordinated atoms and Mn（Ⅱ） ion.

Synthesis and Structural Characterization of Mono-and Di-nuclear Zinc(Ⅱ) Coordination Compounds of Triphenylphosphoniopropionate

Two novel coordination compounds of Zn(Ⅱ) with Ph_3P+(CH_2)_2CO-_2(L), namely, [ZnL_4(H_2O)_2]·(ClO_4)_2·2H_2O(compound 1) and [Zn_2Cl_4(μ-L-O,O′)_2](compound 2), have been prepared. The single crystal X-ray structure analysis of these compounds indicates that in compound 1 the Zn(Ⅱ) atom is coordinated by four monodentate carboxylato groups on the equatorial plane and two aqua ligands occupy the axial coordination positions. The pendant oxygen atoms form strong hydrogen bonds with the aqua molecules which results in the stability of this structure. In compound 2, two Zn(Ⅱ) atoms are bridged by a pair of carboxylato groups, showing a skew-bridge mode, and thus enabling a long Zn(Ⅱ)…Zn(Ⅱ) separation. As we know, it is a dinuclear coordination compound with the longest Zn…Zn separation.

Synthesis and Crystal Structure of a Cu(Ⅱ) Coordination Polymer: [Cu(L)(1,10-phen)]_n

A new complex [Cu（L）（1,10-phen）]n （1, L = N-3-pyridine sulfonyl amino acid） has been synthesized and characterized by IR, elemental analysis and X-ray diffraction analysis, and its crystal belongs to monoclinic, space group P2Jc with a = 11.481 （2）, b = 1 8.094（4）, c = 8.5198（17） ]°, β= 102.26（3）°, V = 1729.5（6） ,/k3, Z = 4, Dc = 1.759 g/cm3, F（000） = 932, p = 1.422 mm-1, R = 0.0368 and wR = 0.0893. In 1, the Cu（ll） ion adopts a slightly distorted five-coordinated square pyramidal geometry. The L2- ligand adopts O of the carboxyl bridging adjacent Cu（Ⅱ）units to form an infinite chain structure along the c axis. Also, π-π stacking interactions between the adjacent chains expanded the 1-D structures into a 3-D supramolecular structure.

Synthesis, Crystal Structure and Electrochemical Properties of a One-dimensional Chain Coordination Polymer [Cu(phen)(2,4,6-TMBA)_2(H_2O)]_n

A one-dimensional chain coordination polymer [Cu（phen）（2,4,6-TMBA）2（H2O）]n has been synthesized by reacting 2,4,6-trimethyl-benzoic acid, 1,10-phenanthroline and Cu（Ⅱ） perchlorate and its structure was characterized. Crystal data for this complex： tetragonal, space group I41, a = 2.0293（3）, b = 2.0293（3）, c = 1.3758（2） nm, α =β= γ = 90°, V= 5.6657（13） nm3, Dc= 1.379 g/cm3, Z = 8, μ（MoKa） = 0.815 mm-1, Mr = 588.14, F（000） = 2456, S = 1.047, R = 0.0459 and wR = 0.1053. The crystal structure shows that two neighboring Cu（Ⅱ） ions are linked together by one bridging-chelating 2,4,6-trimethyl-benzoic group, forming a one-dimensional chain structure. Each Cu（Ⅱ） ion is coordinated with two nitrogen atoms from one 1,10-phenanthroline molecule, three oxygen atoms from three 2,4,6-trimethyl-benzoic acid molecules and one oxygen atom from one water molecule, giving a six-coordinate distorted octahedral coordination geometry. The cyclic voltammetry behavior of the complex was also investigated.

Hydrothermal Synthesis and Crystal Structure of a 1D Cu(II) Coordination Polymer: [Cu(bbpy)(H_2bptc)]_n Constructed by a Tetracarboxylic Acid

The title compound [Cu（bbpy）（H2bptc）]n （bbpy = 4,4＇-dimethyl-2,2＇-bipyridine and H4bptc = 1,1＇-biphenyl-2,2？,3,3＇-tetracarboxylic acid） has been synthesized by hydrothermal reaction, and its structure was determined by X-ray diffraction and characterized by elemental analysis, IR spectrum and thermogravimetric analysis. The crystal is of triclinic, space group P1 with a = 11.2831（12）, b = 11.6718（13）, c = 11.7771（13）, α = 105.392（2）, β = 108.382（2）, γ = 112.397（2）o, CuC28H20N2O8, Mr = 576.00, V = 1222.4（2）3, Dc = 1.565 g/cm3, F（000） = 590, μ = 0.951 mm-1, S = 1.022 and Z = 2. The final refinement gave R = 0.0405 and wR = 0.1142 for 4270 observed reflections with I 2σ（I）. The title complex has a 1D [Cu（bbpy）（H2bptc）]n chain structure, in which the extensive hydrogen-bond interactions make the chain more stable. The neighboring parallel chains are further packed into a 2D layer structure via π···π stacking interaction between the pyridine rings of bbpy ligands. Moreover, the adjacent layers are interconnected by the C–H···π interactions to form a 3D metal-organic framework.

Syntheses, Crystal Structures, and Magnetic Properties of Mn(Ⅱ) and Co(Ⅱ) Coordination Polymers Constructed from Pyridine-tricarboxylate Ligand

Two coordination polymers, namely {[Mn（HL_1）（phen）]·4H_2O}_n（1） and [Co_2（HL_2）_2（H_2O）_2]_n（2） have been constructed hydrothermally using H_3L_1 and H_3L_2（H_3L_1 = 2-（5-carboxypyridin-2-yl）terephthalic acid, H_3L_2 = 2-（4-carboxypyridin-3-yl）terephthalic acid）, phen, MnCl_2×4H_2O and CoCl_2×6H_2O. The products were isolated as stable crystalline solids and were characterized by IR spectroscopy, elemental, thermogravimetric（TGA）, powder（PXRD） and single-crystal X-ray diffraction analyses. Compound 1 features a 3D framework structure, which was topologically classified as a trinodal 4,6,6-connected net with the unique topology defined by the point symbol of（3^（10）.5.6~4）4（3^（10）.6.7~4）2（5.6~2.8~2.9）. Compound 2 possesses a 2D metal-organic layer, which was topologically classified as a binodal 4,4-connected layer defined by the point symbol of（4~3.6~2.8）. The layers are further extended into a 3D supramolecular framework via hydrogen bonds. The magnetic properties for both compounds were also investigated, indicating antiferromagnetic interactions between the adjacent metal ions.

Syntheses and Crystal Structures of Two Copper(Ⅱ) Coordination Polymers Derived from Aromatic Carboxylic Acids and Bis(imidazoles)Ligands

Two compounds have been obtained by the reaction of metal（Cu（II））, 4,4＇-bis（imidazol-l-yl）diphenyl thioether（BIDPT） with two carboxylic acids, 4,4＇-oxydibenzoic acid（H2oba） and phthalic acid（H2pht）. The crystal structures of the resulting compounds, namely {[Cu（BIDPT）（oba）]·H2O}n（1） and {Cu（BIDPT）（pht）}n（2）, have been determined by single-crystal X-ray diffraction analysis. Compound 1 is of orthorhombic system, space group Pbcn with a = 27.8310（3）, b = 10.7791（1）, c = 19.3913（2）A, V = 5817.0（3） ？3 and Mr = 656.15. Compound 2 belongs to the monoclinic system, space group C2/c with a = 18.2678（2）, b = 11.0259（1）, c = 22.906（2） A, β = 97.727（2）o, V = 4571.8（8） A3 and Mr = 545.04. Structural analyses reveal that compounds 1 and 2 respectively exhibit two-dimensional（2D） wavy and corrugated layer structures. Through intermolecular hydrogen bonding, compound 1 is assembled into a 3D supramolecular structure. The thermal stability and ultraviolet spectroscopy properties of the two compounds are also investigated.

Synthesis, Crystal Structure and I2 Capture of a Cd(Ⅱ) Coordination Polymer Based on a Linear Bipyridyl Benzene Ligand

A new complex with formula [Cd（3-pbpmb）2 I2]n 1（3-pbpmb = 1,4-bis（pyridine-3-ylmethoxy）benzene）, has been solvothermally synthesized and characterized. The crystal belongs to monoclinic system, space group P21/n with a = 8.2905（17）, b = 16.078（3）, c = 13.213（3）A, β = 99.44（3）°, Mr = 950.86, V = 1737.3（6） A^3, Z = 2, Dc = 1.818 g/cm^3, F（000） = 924, m = 2.450 mm（-1）, the final R = 0.0198 and w R = 0.0467 for 3053 observed reflections（I ＆gt; 2σ（I））. The Cd（Ⅱ） ion is coordinated by four N atoms of four 3-pbpmb ligands and two iodine ions to furnish a distorted octahedral coordination geometry. The Cd（Ⅱ） ion and its own symmetry-related ions are bridged by N atoms from two 3-pbpmb ligands to generate a ＂zigzag＂ 1-D chain coordination polymer. These 1D chains are further connected into a three-dimensional（3D） framework by C–H×××pinteractions and intermolecular C–H×××I hydrogen bond. Interestingly, 1 displays efficient sorption of molecular iodine gas（up to 111 wt%）, but invalid sorption of molecular water gas.

A 2D Brickwall-like Copper(Ⅱ) Coordination Polymer Based on Phenyliminodiacetate and 4,4?-Bipyridine: Synthesis,Crystal Structure and Magnetic Property

A novel copper（II） coordination polymer of {[Cu3L2（4,4＂-bipy）4]（CIO4）2＂20H20}, （1） was synthesized by the reaction of H2L （C6HsN（CH2COOH）2, phenyliminodiacetic acid）, CuSO4.5H20, NaCIO4.H20 and 4,4＂-bipy （4,4＂-bipyridine） in water/methanol, followed by slow evaporating at room temperature. The compound was characterized by elemental analysis （EA）, infrared spectroscopy （IR）, thermogravimetric analysis （TGA） and single-crystal/powder X-ray diffraction. The result of single-crystal X-ray diffraction analysis reveals that 1 crystallizes in the monoclinic crystal system with C2/c space group, a = 2.9974（4）, b = 1.7270（2）, c = 2.0007（3） nm, fl = 128.793（2）°, V= 8.0722（19） nm3, Z = 4, Dc = 1.472 g.cm-3,/a = 0.942 mm-1, F（000） = 3716, R= 0.0487 and wR = 0.1204 （I 〉 20（/））. The basic structural unit of 1 is a trinuclear cluster unit of [Cu3L2]2＋, which is constructed by two #2-L2- ligands bridging and chelating three Cu（Ⅱ） ions. These [Cu3L2]2＋ units are connected with each other by 4,4＂-bipy ligands to generate a 2D cation brickwall-like network of [Cu3L2（4,4＂-bipy）4]n2n＋. These adjacent 2D cation layers are further stacked in a staggered fashion via interlayer stacking interactions to form a 3D supramolecular structure with 1D open square channels, in which the C104- counter anions and lattice water molecules are filled. Furthermore, the magnetic property of 1 was also investigated.

锌试剂-Cu(Ⅱ)金属配合物与牛血清蛋白作用研究

The interaction of Zincon(ZCN)-Cu(Ⅱ) metal complexe with bovine serum albumin (BSA) was investigated by UV-Vis spectrophotometric method in acidic buffer solution (pH=4.25). ZCN-Cu(Ⅱ)-BSA was a blueness color coordination compound, with maximum absorption at 605 nm with 10 nm, 60 nm and 140 nm of red shift compared to the ZCN-Cu(Ⅱ) complex, ZCN-BSA complex and ZCN. According to molar ratio method and dual wavelength method, the apparent molar absorptivity of ε was equal to 4.82×105 L·mol-1·cm-1. Conditional constants were defined as ZCN∶Cu(Ⅱ)∶BSA=10∶5∶2. Condition combination constant of ZCN-Cu(Ⅱ) and BSA K was 8.82×104. A combined mechanism was suggested between BSA and ZCN-Cu(Ⅱ) by electrostatic force (Primary action force) and distant water force. Position of Impact might be arginine, proline, histidine, tyrosine and cystine. Contemporary formation of electron transfer complexes is an important cause in forming ZCN-Cu(Ⅱ)-BSA complexes.

Cu(Ⅱ)对壳聚糖的配位控制降解

对壳聚糖进行液态均相络合反应制得壳聚糖铜配合物,IR、UV、元素分析及热重分析等检测证实了壳聚糖铜配合物中配位键的存在,且显示壳聚糖在形成配位结构后存在有利于降解的优势构象。以H2O2对壳聚糖-Cu?络合物及壳聚糖进行氧化降解,考察降解过程中粘度的变化及降解产物分子量分布,在相同的降解条件下,壳聚糖铜配合物的降解速度明显高于壳聚糖,降解产物分子量分布较壳聚糖直接降解窄,结果进一步证明壳聚糖铜配合物中存在有利于降解的优势结构,同时证明以金属离子Cu?对壳聚糖的配位控制降解是可以实现的。

不对称氧氮氧三齿配体Cu(Ⅱ)配合物催化NA酯水解研究

合成了不对称氮氧杂链型配体Ｎ－（２′－羟基）苄基乙醇胺（ＨＬ），通过元素分析、ＩＲ和１ＨＮＭＲ等手段进行了表征。用ｐＨ电位滴定法，在２５±０．１℃，Ｉ＝０．１０（ＫＮＯ３）条件下，研究了该配体质子化及其与Ｃｕ（Ⅱ）离子配位热力学。在２５±０．１℃，Ｉ＝０．１０（ＫＮＯ３），ｐＨ＝７～９（５０ｍｏｌ·Ｌ－１缓冲溶液）范围内，通过分光光度法测定了配合物对ｐ－硝基苯酚乙酸酯（ＮＡ）水解催化动力学，得到了ＮＡ酯催化水解二级反应速率常数ｋＮＰ（（ｍｏｌ·Ｌ－１）－１·ｓ－１）。结果表明：Ｃｕ（Ⅱ）离子与醇羟基配位作用较强，并且还与一个水分子有较弱的配位。配位醇羟基和水分子的离解常数ｐＫａ分别为７．６２和１１．２２。在中性ｐＨ值可以产生具有有很强亲核能力的配位烷氧负离子Ｃｕ（Ⅱ）…－ＯＲ，配合物对酯的水解有金属离子Ｌｅｗｉｓ酸活化和亲核试剂进攻双重催化作用，与碱性磷酸酯催化作用比较类似，在ｐＨ中性和弱碱性条件下对ＮＡ酯水解有很好的催化效果，当ｐＨ为９．０时，ｋＮＰ达到０．１２（ｍｏｌ·Ｌ－１）－１·ｓ－１。

二维铜(Ⅱ)配位聚合物{[Cu(1,3-bip)(1,3-bdc)]·H_2O}_n的合成、晶体结构及热稳定性研究

以1,3-bip(1,3-二咪唑丙烷)、1,3-bdc(间苯二甲酸)和Cu(NO3)2·3H2O为原料,在水热条件下合成了二维铜(Ⅱ)配位聚合物{[Cu(1,3-bip)(1,3-bdc)]·H2O}n,并用元素分析、红外光谱、X-射线单晶衍射对配合物进行了表征.测定结果表明,晶体属三斜晶系,P-1空间群,晶胞参数:a=0.910 50(5)nm,b=1.004 65(7)nm,c=1.154 67(6)nm,α=84.924(5)°,β=89.444(4)°,γ=76.505(5)°.标题配合物中每个Cu(Ⅱ)离子作为一个四连接的节点,通过1,3-bdc和1,3-bip桥联连接形成了二维(4,4)网格结构.此外,通过热重分析研究该配合物的热稳定性.

2-呋喃甲醛-4-羟基苯甲酰腙及其Cu(Ⅱ)配合物的晶体结构及与CT-DNA的结合性能

通过2-呋喃甲醛与4-羟基苯甲酰肼缩合得到2-呋喃甲醛-4-羟基苯甲酰腙(H2L),并以其为配体与Cu(Ⅱ)配位得到了配合物[Cu(HL)2]·2H2O(1),采用元素分析和X射线单晶衍射对配体和配合物进行结构表征,结果表明配体属于正交晶系,Pna21空间群。配合物属于单斜晶系,P21/c空间群。利用热重实验研究了H2L和1的热稳定性,并计算了它们主要热分解过程的表观活化能,发现H2L和1的热稳定性都较高。通过紫外吸收光谱研究了H2L和1与CT-DNA的相互作用方式,并利用微量热计测量了其作用过程的热效应,结果表明H2L和1均以插入方式与CT-DNA结合,且作用过程放出的热量1大于H2L,说明配合物与CTDNA的结合能力强于配体。

两个Cu(Ⅱ)配位超分子的研制及光物理性质

采用水热和溶剂热方法合成了2个Cu(Ⅱ)配合物:[Cu(C3H2O4)(phen)(H2O)]2·3H2O(1)和[Cu(inic)2(H2O)3]·H2O(2)(phen=邻菲啰啉;inic=异烟酸根).通过单晶X射线衍射、IR、UV-Vis-NIR吸收光谱、表面光电压光谱(SPS)对其进行了结构表征和物性测试.结构分析表明,2种配合物均为单核Cu(Ⅱ)配合物.配合物(1)中Cu(Ⅱ)离子为五配位,配位环境为畸变的四方锥构型;配合物(2)中Cu(Ⅱ)离子为五配位,配位微环境为畸变的四方锥构型.丰富的分子间氢键将它们网联成了2D配位超分子.2种配合物的SPS在300～800nm范围内都呈现出正的表面光伏响应,表明它们都具有一定的光电转换能力.分析讨论了2种配合物的电子光谱和SPS谱.

2-取代芳基苯并咪唑-Cu(Ⅱ)络合物的研究

合成了 3种 2 取代芳基苯并咪唑 Cu(Ⅱ )络合物 ,通过苯并咪唑与Cu(Ⅱ )反应前后红外光谱解析 ,表明二者发生了络合反应 ;采用摩尔比法测定了该络合反应的配位数、X射线衍射测定了络合物的结构 ,确定了该络合物中心原子Cu(Ⅱ )

一个Cu(Ⅱ)配位超分子的研制及光物理性质

采用水热方法合成了1个新的Cu（Ⅱ）配合物[Cu（pdc）2]＆#183;[（CH3）2 NH2]2（H2 pdc＝吡啶-2，5-二羧酸）．通过X射线单晶衍射确定了该配合物的结构．对配合物进行了IR、固体UV-Vis 吸收光谱、表面光电压光谱（SPS ）和场诱导表面光电压光谱（FISPS ）、热重等物性表征．结构分析表明，该配合物为 Cu （Ⅱ）的单核配合物，其中Cu（Ⅱ）离子为四配位（CuN2 O2配位模式），形成扭曲的平面四边形构型．晶体中，分子间通过Cu…O弱键及氢键网联成3D超分子．SPS结果表明，该配合物在300～800 nm范围内呈现出一定的光电响应，表明它具有一定的光电转换能力．将SPS与UV-Vis光谱进行了关联，发现它们具有密切关系．

新型草酰胺桥联Cu(Ⅱ),Ni(Ⅱ)均双核配合物的合成及表征

合成了一种新配体N ,N′ 二 (2 氨乙基 ) 草酰胺双缩邻氨基苯甲醛Schiff碱 (H4L)及其Cu(Ⅱ )、Ni(Ⅱ )均双核配合物。并用元素分析、红外光谱、电子光谱、室温磁化率等对其组成和结构进行表征。室温磁矩表明配合物中两金属离子间通过草酰胺桥存在着反铁磁性自旋偶合作用。

基于｛XW_(12)O_(40)｝^(4-)(X=Si/Ge)阴离子的二维Cu(Ⅱ)配合物的合成及晶体结构

利用水热合成技术,成功合成了2种基于Keggin阴离子{XW12O40}4-(X=Si/Ge)的Cu(Ⅱ)配合物:H2[{Cu(4,4′-bipy)3/2(OH)(H2O)}2{XW12O40}].4H2O(X=Si,1;X=Ge,2),通过单晶X-射线衍射分析、红外光谱、热重-差热分析及电化学手段对配合物进行了结构表征和基本的性质研究.单晶X-射线衍射分析表明,它们互为异质同构体,晶体结构可描述为Cu(Ⅱ)离子通过OH-基团和4,4′-bipy分子连接形成了一维Z形链,链与链之间进一步通过Keggin阴离子的两个端氧原子与Cu(Ⅱ)离子桥联,形成二维层状结构;沿b轴方向观察1和2的晶体结构,发现邻近的层与层之间距离为14.9.

聚马来松香酰乙二胺-Cu(Ⅱ)配合物的合成及在固定化酶中的应用

介绍了聚马来松香酰乙二胺-Cu(Ⅱ)高分子配合物的制备和固定化香蕉多酚氧化酶的方法,测定了固定化香蕉多酚氧化酶的活性和米氏常数,研究了温度和pH值对固定化香蕉多酚氧化酶催化活性的影响及固定化香蕉多酚氧化酶的重复催化活性。结果表明,聚马来松香酰乙二胺-Cu(Ⅱ)高分子配合物,是香蕉多酚氧化酶的良好固定化载体,固定化香蕉多酚氧化酶的米氏常数Km=4.56×10-3mol.L-1,小于天然香蕉多酚氧化酶的米氏常数(1.95×10-2mol.L-1),固定化香蕉多酚氧化酶的耐热性和耐酸碱性均优于天然香蕉多酚氧化酶,并有一定的重复使用性。对香蕉多酚氧化酶的固定化方式和固定化香蕉多酚氧化酶的催化反应机理也进行了初步探讨。