Synthesis of a New Cobalt （Ⅱ） Complex and its Interaction with DNA

A new complex of bis(N-benzyl benzotriazole-N^3) dichloro Co(Ⅱ) (Co(Ⅱ)L2Cl2) was synthesized and its crystal was characterized. The interaction of this new complex with fs-DNA was studied by electrochemical and UV spectrophotometric method. In 0.01 mol/L pH 4.2 Tris-HCl buffer solution Co(Ⅱ)L2Cl2 has two reductive peaks with peak potentials at 0.38 V and 0.27 V, respectively, and an oxidative peak at 1.05 V. After the addition of DNA, the peak currents decrease and the peak potential at 0.27 V shifts negatively. The UV spectrophotometric experiment indicates that the maximum absorbance of Co(Ⅱ)L2Cl2 at 204 nm decreases and exhibits bathochromic shift after the addition of DNA. All the results reveal that Co(Ⅱ)L2Cl2binds with DNA by intercalation as well as electrostatic interaction.     

两个八氰基W（Ⅳ）-Mn（Ⅱ）双金属配合物的结构及磁性质

合成了两个氰基桥连的异金属配位聚合物[{Mn（dpa）2}2W（CN）8·CH3CN·4H2O]n（1）和[Mn2（H2O）4{W（CN）8}·3H2O]n（2）,并对它们进行了结构和磁性表征．X-射线单晶结构分析表明,在化合物1中,W2（CN）4Mn2四核片段通过公共的[W（CN）8]^4-离子相互连接,形成一个无限延伸的一维链状结构．化合物2的结构较为复杂,是一个含有一维孔道（约13.21A×11．82A）的三维网状结构．磁性研究表明,在两种化合物中,相邻的两个锰离子之间抗磁性的八氰基配离子均传递非常微弱的反铁磁相互作用．     

Syntheses and Crystal Structures of Two Novel Cobalt（Ⅱ） Complexes with 2-Amino-5-substituted-l,3,4-thiadiazole as Ligands

Two novel cobalt（Ⅱ） compounds were obtained and characterized by X-ray sing- le-crystal diffraction, IR, 1H NMR and elemental analysis. Compound 1 crystallizes in monoclinic, space group P21/n, with a = 18.046（4）, b = 11.335（3）, c = 19.157（5）A, β = 92.707（3）°, Z = 4, V = 3914.4（16） A3, Mr = 968.56, Dc = 1.644 g/cm3, μ = 1.378 mm^-1, F（000） = 1960, the final R = 0.0367 and wR = 0.0895. The crystal of compound 2 is of monoclinic, space group P211c with a = 8.7253（10）, b = 10.9031（13）, c = 18.235（2）A,β = 93.2210（10）°, Z = 4, V = 1732.0（3）A3, Mr = 464.21, Dc = 1.780 g/cm3,μ = 1.560 mm-1, F（000） = 932, the final R = 0.0322 and wR = 0.0743.     

Dioxygen Affinities and Catalytic Oxidation Performance of Cobalt （Ⅱ）Complexes with N—Aryl Hydroxamic Acid

The oxygenation of cobalt(Ⅱ) hydroxamates(CoL2) and its catalytic performance in oxidation of p-xylene to p-toluic acid (PTA) were examined.The effects of X and Y bonded to hydroxamate group on dioxygen affinities and catalytic oxidation performance were also investigated.     

Synthesis,Crystal Structure and Characterization of a Cobalt Coordination Polymer： [Co（1,4-ndc）（L） （H2O）]n

The title coordination polymer, [Co（1,4-ndc）（L）（H2O）]n 1 （1,4-H2ndc = 1,4-na- phthalenedicarboxylic acid and L =1-（5-（1H-imidazol- 1-yl）pentyl）- 1H-imidazole） has been hydrothermally synthesized and characterized by IR and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/n with a = 12.4333（12）, b = 13.2963（13）, c = 13.4678（13）A, α =β = 90°, y =107.302（2）°, V= 2125.7（4）A^3, Z = 4, CoC22H22N4O5, Mr = 481.37, De = 1.504 g/cm^3, F（000） = 996, μ（MoKa） = 0.850 mm^-1, R = 0.0472 and wR = 0.0984. Compound 1 exhibits a two-dimensional layer structure. The O-H...O and C-H...O hydrogen bonds stabilize the structure of 1.     

Synthesis and Crystal Structure of a Binuclear Cobalt（ Ⅱ） Carboxyla

Reaction of cobalt carbonate, pivalic acid and quinoline in a refluxing ethanol solvent yielded the dicobalt(Ⅱ) compound, Co2(O2CCMe3)4(C9H7N)2 (1) (C9H7N is quinoline), which has been characterised by elemental analysis, IR and X-ray diffraction method. Crystallographic data: monoclinic, P21/a, a=9.341(2), b=18.591(4), c=11.822(2)(), β=97.71(2), V=2034(1)()3, Z=2, Mr=918.19, Dc=1.27 g/cm-3, F(000)=820, μ(MoKα)=8.60 cm-1, T=293K, final R=0.049, Rw=0.060 for 2715 observed reflections with I>3.0 σ(I). The centrosymmetric molecule comprises a pair of cobalt(Ⅱ) atoms connected by four pivalate ligands in syn-syn bridging modes. Square pyramidal five-coordination of cobalt(Ⅱ) is further completed by a quimoline molecule. The CoⅡ-CoⅡ distance is 2.784(1)().     

Ionothermal Syntheses and Crystal Structures of Two Cobalt（Ⅱ） Compounds：Co（2,2＇-bpy）_2Br_2 and Co（1,10-phen）_2Br_2

Two cobalt(Ⅱ) compounds,Co(2,2-bpy) 2 Br 2 (1,2,2-bpy=2,2-bipyridyl) and Co(1,10-phen) 2 Br 2 (2,1,10-phen=1,10-phenanthroline),have been prepared under ionothermal reactions using the 1-propyl-3-methylimidazolium bromide ionic liquid solvent.Single-crystal X-ray analyses reveal that 1 crystallizes in a monoclinic space group P2 1 /c,with a=8.5509(13),b=14.804(2),c=15.650(2),β=97.119(2) o,V=1965.8(5) 3,Z=4,C 20 H 16 Br 2 N 4 Co,M r=531.12,D c=1.795 g/cm 3,μ=4.950 mm-1,F(000)=1044,the final R=0.0467 and wR=0.0736 for 2291 observed reflections with I > 2σ(Ⅰ).Complex 2 crystallizes in a monoclinic space group P2 1 /n,with a=10.4237(8),b=16.8657(12),c=12.4945(9)b,β=102.110(1) o,V=2147.7(3) 3,Z=4,C 24 H 16 Br 2 N 4 Co,M r=579.16,D c=1.791 g/cm 3,μ=4.540 mm-1,F(000)=1140,the final R=0.0431 and wR=0.1042 for 3470 observed reflections with I > 2σ(Ⅰ).The mononuclear molecules of 1 are linked by the C-H···Br hydrogen bonds and π-π interactions to form a three-dimensional supramolecular framework structure.The C-H···Br hydrogen bonds and π-π interactions link the mononuclear molecules of 2 to give a two-dimensional layer structure.     

Ferroelectricity based on coordination compound： Transition metal Co（Ⅱ） sulfates templated by homochiral 2-methylpiperazine （C5H14N2）[ Co（H2O）6]（SO4）2

Reacting homochiral （R）-2-methylpiperazine with cobalt sulfate heptahydrate by the solution method in the presence of concentrated sulfuric acid （H2SO4） yielded two coordination compounds （C5H14N2） [CO（H2O）6]（SO4）2 （1 and 2）. They are polymorphs, but their hydrogen bonds structure differ significantly. Both 1 and 2 crystallize in chiral space group P21 which is related with point group C2, and experimental results suggest that 1 displays ferroelectric behaviors.     

金属间化合物Y（Fe1—xCox）11.3Nb0.7的磁性能机制研究

通过X射线衍射和磁笥测量方法研究了金属间化合物Y（Fe1-xCox)11.3Nb0.7（x=0,0.05,0.10,0.20）的结构与磁性能。粉末样品的X射线衍射和热磁曲线测量表明,所有Y（Fe1-xCox)11.3Nb0.7（x=0,0.05,0.10,0.20）化合物具有ThMn12型结构,具有良好的单相性,Co替代Fe引起居里温度显著提高和晶格常数的单调减小,室温下的饱和磁化强度M。随Co含量的增加在x=0.1-0.2之间呈现极大值,各向异性场Ba随x的增加,先增加而后减小。     

Structure and Photosynthetic Mimicking of Bis（2,6—bis（benzimidazol—2—yl）pyridine）manganese（Ⅱ）

Mn(bzimpy)2(1)[bzimpy=2,6-bis(benzimidazol-2-yl)pyridine],a mononuclear manganese(Ⅱ）complex,was synthesized by the reaction of Mn(OOCMe)2 with bzimpy in absolute ethanol.The complex was structurally characterized by elemental analysis,cyclic voltammetry,and X-ray crystallography.In the complex,the manganese-nitrogen distances were different,and the geometry and the metal ion environment showed the distortion.The cyclic voltammetric measurements have been performed to assess its redox characteristics.The presence of oxidation wave at 0.62V and 0.081V vs.SCE or 0.8V and 1.0v vs.NHE suggested that this complex could catalyze the oxidation of water,therefore,simulate the water-oxidizing complex(WOC) of photosystem Ⅱ (PS Ⅱ).The measurements of photoreduction of 2,6-dichlorophenolindophenol (DCPIP),and oxygen evolution in the manganess-depleted and the comples 1-reconstituted PS Ⅱ preparations just support our conjecture.     

Synthesis and Crystal Structure of a Novel Cobalt（Ⅱ） Coordination Polymer with 1,2,4,5-Benzenetetracarboxylate

A novel cobalt（II） coordination polymer,[Co（BTEC）1/2]n 1,has been synthesized with Co（NO3）2·6H2O and 1,2,4,5-benzenetetracarboxylic acid （H4BTEC） by the hydrothermal method,and characterized by elemental analysis,IR and single-crystal X-ray diffraction. Crystallographic data for 1： C5HO4Co,Mr = 183.99,monoclinic,space group C2/c,a = 16.619（6）,b = 7.416（3）,c = 8.040（3）A,β = 90.612（4）°,V = 990.8（6） A^3,Z = 8,Dc = 2.467 g/cm^3,μ = 3.390 mm^-1,F（000） = 720,R = 0.0307 and wR = 0.0847 for 912 observed reflections （I 〉 2σ（I））. X-ray crystal structural analysis revealed that each Co（II） adopts a tetrahedral coordination mode to link four separate BTEC ligands via uniform monodentate carboxylate groups and each BTEC ligand possesses an 8-connected geometry to connect eight Co（II） ions. Complex 1 exhibits a rare （4,8）-connected net with （45.6）2（410.614.84） topology.     

含CS配体的单、双核钌羰基化合物Ru（CS）（CO）n（n=4,3）和Ru2（CS）2（CO）n（n=7,6,5,4）的理论研究

采用2种密度泛函方法MPW1PW91和BP86对中性单核Ru(CS)(CO)n(n=4,3)及双核Ru2(CS)2(CO)n(n=7,6,5,4)化合物进行理论计算研究,优化出25个异构体.研究发现,单核配位饱和Ru(CS)(CO)4的2个异构体14-1,14-2能量接近,其配体呈三角双锥型.对称性为C2v的异构体14-1能量稍低,其CS基团在三角双锥赤道面上.单核配位不饱和Ru(CS)(CO)3的能量最低异构体是由14-1失去1个赤道面上的CO得到的,其对称性为Cs.配位饱和的双核Ru2(CS)2(CO)7能量最低异构体27-1结构中有3个桥配位基团,其中2个是CS基团.配位不饱和的Ru2(CS)2(CO)6存在2个能量接近的异构体,即含3个桥配位基团对称性为Cs的异构体26-1和含2个桥配位基团的异构体26-2.它们的CS基团都是桥配位形式.Ru2(CS)2(CO)5的能量最低异构体25-1含有两个桥配位CS基团,其中一个是4电子供体.而Ru2(CS)2(CO)4的能量最低异构体24-1的两个桥配位CS基团都是4电子供体.在上述各个异构体中,单核Ru(CS)(CO)n(n=4,3)的能量最低异构体的CS基团都位于配体三角双锥及缺顶点结构的赤道面上,双核Ru2(CS)2(CO)n(n=7,6,5,4)能量最低异构体的CS基团都以桥配位形式和Ru原子相连,且在配位不饱和Ru2(CS)2(CO)n(n=5,4)的能量最低异构体中都存在4电子供体CS基团.离解能研究表明,单核配位饱和的Ru(CS)(CO)4具有一定的热力学稳定性.双核的Ru2(CS)2(CO)n(n=7,6,5)失去1个CO或者分裂为单核的Ru(CS)(CO)4或Ru(CS)(CO)3所需能量都较高,但Ru2(CS)2(CO)6和Ru2(CS)2(CO)5有发生歧化反应的趋势,而Ru2(CS)2(CO)7具有一定的热力学稳定性.     

Hydrothermal Synthesis and Crystal Structure of a Manganese（Ⅱ） Complex：Mn_（1.5）（cbba）_3（phen）

A new metal-organic complex Mn1.5(cbba)3(phen)(Hcbba = 2-(4'-chlorine-ben-zoyl)benzoic acid,phen = 1,10-phenanthroline) 1 has been hydrothermally synthesized and struc-turally characterized by single-crystal X-ray diffraction,elemental analyses,TG and IR spectro-scopy.The compound crystallizes in triclinic,space group P1 with a = 12.137(2),b = 14.535(3),c = 14.894(3),α = 86.380(3),β = 70.381(3),γ = 72.647(3)°,V = 2360.3(8)3,C107H64Cl6Mn3N4O18,Mr = 2071.14,Dc = 1.457 g/cm3,μ(MoKα) = 0.638 mm-1,F(000) = 1055,Z = 1,the final R = 0.0638 and wR = 0.1905 for 6155 observed reflections(I > 2σ(I)).It exhibits a 3D supramolecular network through hydrogen bonding and π-π stacking interactions.     

La（Ⅲ）、Nd（Ⅲ）与甜菜碱类衍生物形成的包含（H2O）6分子簇的配合物的晶体结构

利用配体1,5-二(3-羧基吡啶基)-N-甲基二乙胺(L)合成2种稀土金属配合物{[La2L4(H2O)2](ClO4)6·6H2O}n(1)和[Nd2L4(DMF)6(H2O)2]2(ClO4)6·4H2O(2)。用红外光谱和X-射线单晶衍射表征配合物的晶体结构。结构分析表明:配合物1属于三斜晶系,P1空间群,其晶胞参数为a=1.496 6(3)nm,b=1.559 7(4)nm,c=1.956 8(4)nm,α=86.776(6)°,β=77.723(7)°,γ=87.168(7)°,Z=2。在配合物1中,一对La髥原子被2个羧基桥联,形成双核结构;双核结构进一步被羧基连接,从而形成平行于c轴的一维链。值得注意的是配合物1的晶体结构中包含着由氢键连接的6个H2O分子组成的水分子簇。配合物2属于三斜晶系,P1空间群,晶胞参数为a=1.040 8(4)nm,b=1.354 1(5)nm,c=2.975(1)nm,α=94.390(8)°,β=91.720(7)°,γ=95.230(4)°,Z=2。配合物2中4个羧基连接一对Nd髥原子,形成四轮状结构,其中2个羧基采取syn-syn双原子桥联模式,而其余2个羧基则采取单原子桥联模式。     

Synthesis,Crystal Structure and Magnetic Properties of a Ni（Ⅱ） Supramolecular Complex Based on Aromatic Polycarboxylate Ligand

A Ni(Ⅱ) supramolecular complex,[Ni 2 (btec)(3py) 2 (H 2 O) 8 ](H 2 O) 4 (1),has been synthesized by Ni(ClO 4) 2 ·6H 2 O,benzene-1,2,4,5-tetracarboxylic acid (H 4 btec) and terminal ligand 3-hydroxypyridine (3py) in aqueous solution.The title compound crystallizes in triclinic system,space group P1,with a=8.5637(12),b=9.4138(13),c=10.3611(14),α=67.9540(10),β=85.1740(10),γ=76.9890(10)°,V=754.33(18) 3,Z=2,M r=386.96,D c=1.704 Mg/m 3,μ=1.345 mm-1,F(000)=402,the final R=0.0222 and wR=0.0563 for 2675 observed reflections with I > 2σ(Ⅰ).The adjacent discrete molecules are further self-assembled by intermolecular π-π and O-H···O hydrogen bonding interactions to construct a 3D supramolecular framework.Magnetic measurement shows weak ferromagnetic interaction in the range of 2～300 K.     

Synthesis and Crystal Structure of a Cobalt（Ⅱ） Coordination Polymer with Benzene-1,3,5-triacetate and 1,2-Di（pyridin-4-yl）ethene

A novel coordination polymer, [Co3(bta)2(dpe)3(H2O)2]·2H2O (1, H3bta = benzene-1,3,5-triacetic acid, and dpe = 1,2-di(pyridin-4-yl)ethene), has been hydrothermally prepared and characterized by IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. The crystal is of triclinic system, space group P , with a = 9.5687(15), b = 11.2470(17), c = 13.686(2) , α = 78.262(3), β = 89.271(4), γ = 81.292(3)°, V = 1425.2(4) 3, C60H56N6O16Co3, Mr = 1293.90, Dc = 1.508 g/cm3, F(000) = 667, μ = 0.940 mm-1 and Z = 1. The final R = 0.0707 and wR = 0.1413 for 4950 observed reflections (I > 2σ(I)). In the title complex, the bta ligand acts as a four-dentate bridging ligand to link up cobalt atoms into lamellar frameworks which are further interlinked by the dpe ligands to generate a trinodal (3,4,6)-connected (4.62)2(42.68.83.102)(64.82) net.