一个双核镍配合物[Ni2(Htda)2(H2O)6]·4H2O的合成、晶体结构和性质

双核金属配合物对于生物化学和磁化学都是非常重要的。在本文中,1,2,3-三氮唑-4,5-二羧酸(H₃tda)配体和硝酸镍在常温常压下反应得到了1个三氮唑桥联的双核镍配合物[Ni₂(Htda)₂(H₂O)₆]·4H₂O (1),并通过元素分析、红外光谱、X-射线单晶衍射、热重分析以及超导量子干涉仪(SQUID)对其晶体结构和磁、热性质进行了表征。晶体数据表明该配合物属三斜晶系,空间群为P1。在配合物1中,2个1,2,3-三氮唑-4,5-二羧酸配体利用2个相邻的氮原子桥联2个金属镍离子形成一个双桥的双核镍配合物。这些双核镍单元又通过体系中存在的大量的氢键相互作用形成了三维超分子骨架。磁性分析显示双核镍单元内镍镍之间存在反铁磁相互作用。     

基于半刚性四面体四齿配体构筑的Zn(Ⅱ)/Cd(Ⅱ)配位聚合物及其性质

在水热的条件下,利用四(4-吡啶氧甲基)甲烷(L₁)或四(3-吡啶氧甲基)甲烷(L₂)、1,4-萘二甲酸(1,4-NDC)和d¹⁰金属离子发生自组装反应合成了2个化合物{[Cd₂(L₁)(1,4-NDC)₂]·2H₂O}_n(1)和{[Zn₂(L₂)(1,4-NDC)₂]·DMF·3H₂O)}_n(2)。单晶结构表明化合物1是通过L₁配体与一维链[Cd(1,4-NDC)]_n相连构建而成的三维骨架化合物,而化合物2是一对螺旋链与另外的一维链相互垂直交联而形成二维网络结构。更为重要的是,通过引入2种不同空间位阻的配体,研究了辅助配体对金属有机配位聚合物结构多样性的影响。另外,它们的荧光性质也做了相应的探讨。     

A Lanthanide-transition Metal Coordination Polymer：{[CuEu（Hbidc）_2（H_2O）_4]·H_2O}_n（H_3bidc=1H-benzimidazole-5,6-dicarboxylic Acid）

The title complex 1,{[CuEu(Hbidc)2(H2O)4]·H2O}n(H3bidc = 1H-benzimidazole-5,6-dicarboxylic acid),has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1,with a = 7.791(2),b = 12.058(3),c = 12.109(3),α = 82.189(5),β = 72.407(5),γ = 89.184(4)°,V = 1073.7(5)3,C18H18CuEuN4O13,Mr = 713.86,Dc = 2.208 g/cm3,μ(MoKα) = 3.967 mm-1,F(000) = 700,GOOF = 0.950,Z = 2,the final R = 0.0531 and wR = 0.1068 for I > 2σ(I).Complex 1 possess a tape-like chain structure consisting of Eu2C8O4 and Cu2Eu2C18N4O4 metallic rings alternatively arranged and is the first 3d-4f heterometallic complex based on the 1H-ben-zimidazole-5,6-dicarboxylato ligand(Hbidc).Plenty of hydrogen-bonding and π...π stacking interactions connect the 1D chains to construct a 3D supramolecular architecture.     

两个Fe(II)配合物的合成、结构、磁性和穆斯堡尔谱 —— 配合物[Fe(dpq)(Mepy)2(NCS)2]的室温自旋交叉行为

设计制备了两个新的配合物[Fe(dpq)(Mepy)2(NCS)2](1)和[Fe(Medpq)(Mepy)2 (NCS)2](2)。室温下X衍射结果表明配合物（2）为正交晶系,晶胞参数为a = 15.057(3) Å, b = 14.569(3) Å, c = 13.180(3) Å, a = 90.00°, b=90.00°, g = 90.00°。[FeN6] 变型八面体构型中,两个NCS-与其顺式配位,其余四个氮分别来自Medpq和两个Mepy。变温磁化率和穆斯堡尔谱学的研究表明配合物（1）（2）存在自旋交叉,配合物（1）的自旋转换温度为 T1/2 =340K,而配合物（2）在低温条件下的转换是不完全的。     

Synthesis,Structure and Property of a Metal-organic Framework Based on 9-(2,6-Dicarboxy-pyridin-4-yl)-9H-carbazole-3,6-dicarboxylic Acid

A new terbium(III) metal-organic framework [Tb(HL)(H2O)](Tb L) based on a new synthetic ligand 9-(2,6-dicarboxy-pyridin-4-yl)-9 H-carbazole-3,6-dicarboxylic acid(H4 L) has been synthesized under solvothermal conditions. Its structure was determined by single-crystal X-ray diffraction analysis, and further characterized by powder X-ray diffraction analysis and IR spectra. The title complex crystallizes in trigonal space group P3212 with a = b = 13.6491(11), c = 32.345(3) ?, γ = 120°, V = 5218.5(10) ?~3, C(42)H(20)N4O(17)Tb2, Mr = 1170.46, Dc = 1.117 g/cm^3, μ(Mo Kα) = 2.065 mm^-1, F(000) = 1698, GOF = 1.054, Z = 3, the final R = 0.0384 and wR = 0.0771 for 5223 observed reflections(I > 2s(I)). In Tb L, the tri-bridged binuclear Tb2 units are bibridged by two carbazole-3,6-dicarboxylate moieties to lead to the homochiral parallel arranged helical chains, which are further connected by 2,6-pyridinedicarboxylate moieties to produce the chiral neutral 3 D framework. There are there kinds of 1 D channels in the framework with the channel space occupying 53.3% of the total volume. TbL exhibits intense characteristic green emission of Tb³⁺ ions.     

Synthesis, Structure and Physical Properties of Mn and Cd Complexes with 1,1,2,2-Tetracarboxyl-ethylene Acid

Complex [Mn(tce) 0.5(H2O) 4](1) was obtained from Mn(OAc) 2 and tce,where tce is 1,1,2,2-tetracarboxyl-ethane. The structure of 1 is a single molecule,in which Mn(II) is a distorted octahedron coordinated to six oxygen atoms. Complex [Cd(tce) 0.5(H2O) 3](H2O) (2) fea-tures a pillared layer architecture. The Cd(II) atom is in an octahedral environment coordinated by six oxygen donors from water molecules and tce ligands. Cd(II) atoms are interlinked by the tce ligand to generate a 2-D wavelike layer. The layers are strutted by the intermolecular O-H···O hydrogen bonds to form a 3-D open framework. Luminescence property of complex 2 was investigated. Magnetic property of complex 1 was also studied. 1 belongs to triclinic,space group P1 with a = 6.2901(12) ,b = 8.0212(15) ,c = 8.0769(15) ,α = 108.522(3) ,β = 95.068(3) ,γ = 97.086(3) °,V = 379.92(12) 3,Mr = 456.08,Dc = 1.993 g/cm3,F(000) = 232,μ = 1.748 mm-1,Z = 1,the final R = 0.0297 and wR = 0.0731 for 1575 observed reflections with I > 2σ(I) . 2 is of monoclinic system,space group P21/c with a = 6.4367(14) ,b = 9.495(2) ,c = 13.907(3) ,β = 117.405(8) °,V = 754.6(3) 3,Mr = 285.51,Dc = 2.513 g/cm3,F(000) = 556,μ = 2.905 mm-1,Z = 4,the final R = 0.0375 and wR = 0.0737 for 1521 observed reflections with I > 2σ(I).     

Anisotropic self-diffusion of fluorinated poly(methacrylate) in metal-organic frameworks assessed with molecular dynamics simulation

Utilizing the periodically structured metal–organic framework(MOF) as the reaction vessel is a promising technique to achieve the aligned polymer molecular chains, where the diffusion procedure of the polymer monomer inside MOF is one of the key mechanisms. To investigate the diffusion mechanism of fluorinated polymer monomers in MOFs, in this paper the molecular dynamics simulations combined with the density functional theory and the Monte Carlo method are used and the all-atom models of TFMA(trifluoroethyl methacrylate) monomer and two types of MOFs, [Zn_2(BDC)_2(TED)]n and[Zn_2(BPDC)_2(TED)]n, are established. The diffusion behaviors of TFMA monomer in these two MOFs are simulated and the main influencing factors are analyzed. The obtained results are as follows. First, the electrostatic interactions between TFMA monomers and MOFs cause the monomers to concentrate in the MOF channel, which slows down the monomer diffusion. Second, the anisotropic shape of the one-dimensional MOF channel leads to different diffusion speeds of monomers in different directions. Third, MOF with a larger pore diameter due to a longer organic ligand, [Zn_2(BPDC)_2(TED)]n in this paper, facilitates the diffusion of monomers in the MOF channel. Finally, as the number of monomers increases, the self-diffusion coefficient is reduced by the steric effect.     

一个双核镍配合物[Ni2(Htda)2(H2O)6]·4H2O的合成、晶体结构和性质

双核金属配合物对于生物化学和磁化学都是非常重要的.在本文中,1,2,3-三氮唑-4,5-二羧酸(H3tda)配体和硝酸镍在常温常压下反应得到了1个三氮唑桥联的双核镍配合物[Ni2(Htda)2(H2O)6]·4H2O(1),并通过元素分析、红外光谱、X-射线单晶衍射、热重分析以及超导量子干涉仪(SQUlD)对其晶体结构和磁、热性质进行了表征.晶体数据表明该配合物属三斜晶系,空间群为P(1).在配合物1中,2个1,2,3-三氮唑-4,5-二援酸配体利用2个相邻的氮原子桥联2个金属镍离子形成一个双桥的双核镍配合物.这些双核镍单元又通过体系中存在的大量的氢键相互作用形成了三维超分子骨架.磁性分析显示双核镍单元内镍镍之间存在反铁磁相互作用.     

A Copper（Ⅱ）-cadmium（Ⅱ） Heterometallic Hexanuclear Complex：[Cd_4Cu_2（pdc）_4（H_2O）_（14）]（H_3pdc=3,5-Pyrazoledicarboxylic Acid）

The title complex 1,[Cd 4 Cu 2 (pdc) 4 (H 2 O) 14 ] (H 3 pdc=3,5-pyrazoledicarboxylic acid),has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1 with a=0.67235(10),b=1.27935(18),c=1.28569(17) nm,α=112.633(2),β=102.971(3),γ=97.089(2)o,V=0.9673(2) nm 3,C 20 H 32 Cd 4 Cu 2 N 8 O 30,M r=1441.22,D c=2.474 g/cm 3,μ(MoKα)=3.356 mm 1,F(000)=698,S=1.003,Z=1,the final R=0.0471 and wR=0.0748 for I > 2σ(Ⅰ).In 1,two deprotonated 3,5-pyrazoledicarboxylic acids (pdc 3),one copper(Ⅱ) ion and one cadmium(Ⅱ) ion firstly form a pyrazole-bridged Cu II Cd II dinuclear unit,two of which related by an inversion center are connected by another two cadmium(Ⅱ) ions through chelating carboxylate groups to construct the copper(Ⅱ)-cadmium(Ⅱ) heterometallic hexanuclear complexes.Plenty of hydrogen bond interactions existing in the system further lead to a three-dimensional (3D) supramolecular framework.     

基于半刚性四面体四齿配体构筑的Zn(Ⅱ)/Cd(Ⅱ)配位聚合物及其性质

在水热的条件下, 利用四(4-吡啶氧甲基)甲烷(L₁)或四(3-吡啶氧甲基)甲烷(L₂)、1, 4-萘二甲酸(1, 4-NDC)和d¹⁰金属离子发生自组装反应合成了2个化合物{[Cd₂(L₁)(1, 4-NDC)₂]·2H₂O}_n (1)和{[Zn₂(L₂)(1, 4-NDC)₂]·DMF·3H₂O)}_n (2)。单晶结构表明化合物1是通过L1配体与一维链[Cd(1, 4-NDC)]_n相连构建而成的三维骨架化合物, 而化合物2是一对螺旋链与另外的一维链相互垂直交联而形成二维网络结构。更为重要的是, 通过引入2种不同空间位阻的配体, 研究了辅助配体对金属有机配位聚合物结构多样性的影响。另外, 它们的荧光性质也做了相应的探讨。