基于5-(4-(2,6-二(2-吡嗪基)-4-吡啶基)苯氧基)间苯二甲酸的Mn(Ⅱ)和Ca(Ⅱ)配位聚合物的合成与晶体结构

采用对苯二甲酸为模板剂,溶剂热法合成了2个以5-(4-(2,6-二(2-吡嗪基)-4-吡啶基)苯氧基)间苯二甲酸(H₂L)为配体的金属-有机配位聚合物：{[MnL] ·0.5H₂O}_n (1),{[CaL(H₂O)₂]·H₂O}_n (2)。通过X-射线单晶衍射,元素分析和红外光谱进行了结构表征。结构分析表明,1具有(3,3)-连接的不同手性型二维层面结构,这些交替出现的单手性左旋型和右旋型二维平面通过配体的吡啶环与吡嗪环间π…π堆积作用构成了三维超分子结构;2是通过L^2-配体羧基桥连接相邻的Ca(Ⅱ)金属中心,形成一条平行于b轴方向的一维链结构。研究了配位聚合物的热稳定性和2的荧光性质。     

基于5-磺酸基间苯二甲酸钠和双三唑烷烃的Cu(Ⅱ)配合物的合成、结构和性质

利用5-磺酸基间苯二甲酸钠(NaH₂sip)和双三唑烷烃,合成了3个配合物[Cu_0.5(btm)(H₂O)](H₂sip)·H₂O}_n(1,btm=双三唑甲烷),{[Cu(btp)₂(H₂sip)(H₂O)](NO₃)·4H₂O}_n(2,btp=双三唑丙烷)和{[Cu(btb)₂(Hsip)]_n(3,btb=双三唑丁烷)。化合物1为一维双链结构;化合物2为二维四方网络结构,多个二维层依次叠加形成三维超分子结构;化合物3也具有二维层状结构,其中金属铜离子和双三唑丁烷构成的一维双链结构经双齿μ₂-Hsip^2-配体连接构成了二维层状结构。同时对配合物的热稳定性和顺磁共振特性进行了讨论。     

A New Acentric Heterometallic Inorganic-organic Hybrid Framework [ZnK2（m-BDC）2（H20）2]n： Fluorescent,NLO and Ferroelectric Properties

Solvothermal reactions of Zn（NO3）2·6H20 with isophthalic acid in the presence of potassium nitrate lead to an acentric three-dimensional （3D） hereto-metallic inorganic-organic hybrid framework [ZnK2（m-BDC）ffH20）2]n （1, m-H2BDC = benzene-l,3-dicarboxylic acid）. The crystal was characterized by elemental analysis, IR spectroscopy, TGA and single-crystal X-ray diffraction analysis. Complex 1 is of orthogonal crystal system, acentric space group Cmc2j with a = 19.764（6）, b = 19.948（6）, c = 12.039（4） A, V = 4746（3） A3, Z = 4, C32H20019KaZn2, Mr = 995.66, Dc= 1.393 g/cm3, F（000） = 2000 andp = 1.426 mm-1. The final R = 0.0761 and wR = 0.1841. The crystal exhibits remarkable blue luminescence emissions with high quantum yield of 56.02% and displays modest powder SHG efficiency of about 0.7 times that produced by a potassium dihydrogen phosphate （KDP） powder. In addition, it also exhibits potential ferroelectric property.     

Hydrothermal Synthesis and Crystal Structure of One 3D Coordination Polymer of Nickle （II） Achieved from 5-Iodo-isophthalic Acid Ligand

A new coordination polymer [Ni（L）（m-bix）（H2O）]n （1, H2L = 5-iodo-isophthalic acid, m-bix=1,3-bis（imidazol-1-ylmethyl）-benzene） has been synthesized by the hydrothermal method and characterized by IR, elemental analysis, powder XRD and single-crystal X-ray analysis. The crystal is of triclinic, space group Pī with a = 9.1638（3）, b = 10.2319（3）, c = 13.2463（4） ？, α = 80.1710（10）, β = 83.671（2）, γ = 70.3790（10）o,C22H19NiIN4O5, Mr = 605.02, V = 1150.85（6） ？3, Dc = 1.746 g/cm3, F（000） = 600, μ = 2.225 mm-1, S = 1.045 and Z = 2. The final R = 0.0388 and wR = 0.1257 for 5089 observed reflections with I 〉 2σ（I）. In the title complex, the M and P layers are arranged alternately to give a double-layer structure by the symmetry related hydrogen bonds, and these double-layers are further joined together to achieve a 2D supramolecular architecture through I···π interaction involving iodine atoms and imidazole rings. The thermal stability of the title complex was studied by thermal gravimetric （TG） and differential thermal analysis （DTA）.     

Structure and Luminescent Properties of the First Cadmium Complex with Isophthalate and Di-pyrazole Ligands

The title complex [Cd(IPA)L(H2O)]n(1,H2IPA = isophthalic acid,L = 1,4-bis(pyra-zole-1-ylmethyl)benzene) has been hydrothermally synthesized,and characterized by elemental analyses,IR spectroscopy,TGA and X-ray single-crystal diffraction.It crystallizes in the triclinic system,space group P1 with a = 9.3060(6),b = 10.2374(7),c = 11.9706(8) ,α = 73.804(6),β = 77.883(5),γ = 85.942(5)°,V = 1070.7(1) 3,Z = 2,C22H20CdN4O5,Mr = 532.82,Dc = 1.653 g/cm3,μ = 1.062 mm-1,λ(MoKα) = 0.71073 ,F(000) = 536,R = 0.0392 and wR = 0.0640 for 3751 observed reflections with I > 2σ(I).Crystal structure analysis showed that complex 1 has a 1D double chain structure,which is assembled together through strong O-H...O hydrogen bonding interactions between coordinated water molecules and carboxylate groups of isophthalate to form a 2D supramolecular network.In addition,the solid-state fluorescent spectrum of 1 exhibits strong emission at 364 nm.     

Synthesis,Crystal Structure and Characterization of a Ni(Ⅱ) Complex of Constructed 2,6-Bis(benzimidazol-2-yl) pyridine

A fluorescent Ni(II) complex 1, [Ni(OH-H2Bdc)(Bibimp)]n·nH2O, constructed with 5-hydroxyisophthalic acid(OH-H2Bdc) and 2,6-bis(2-benzimidazolyl)pyridine)(Bibimp) has been synthesized by hydrothermal methods and structurally characterized by elemental analysis, IR spectroscopy, TG/DTG, fluorescence spectrum and single-crystal X-ray diffraction. The title complex crystallizes in triclinic system, space group P1 with a = 10.187(2), b = 10.273(2), c = 13.401(3), α = 69.65(3), β = 69.66(3), γ = 70.61(3)o, V = 1196.8(4) 3, and Z = 2. The adjacent chains of complex 1 are stacked offset with respect to each other in an ABAB fashion by van der Waals interactions, and only a weak interlayer nonclassical C–H···O hydrogen bond has been observed. Complex 1 displays strong blue fluorescent emissions at 483 nm in the solid state upon photo-excitation at 365 nm at room temperature.     

基于5-(4-(2,6-二(2-吡嗪基)-4-吡啶基)苯氧基)间苯二甲酸的Mn(Ⅱ)和Ca(Ⅱ)配位聚合物的合成与晶体结构

采用对苯二甲酸为模板剂, 溶剂热法合成了2个以5-(4-(2, 6-二(2-吡嗪基)-4-吡啶基)苯氧基)间苯二甲酸(H₂L)为配体的金属-有机配位聚合物:{[MnL] ·0.5H₂O}_n (1), {[CaL(H₂O)₂]·H₂O}_n (2)。通过X-射线单晶衍射, 元素分析和红外光谱进行了结构表征。结构分析表明, 1具有(3, 3)-连接的不同手性型二维层面结构, 这些交替出现的单手性左旋型和右旋型二维平面通过配体的吡啶环与吡嗪环间π…π堆积作用构成了三维超分子结构;2是通过L^2-配体羧基桥连接相邻的Ca(Ⅱ)金属中心, 形成一条平行于b轴方向的一维链结构。研究了配位聚合物的热稳定性和2的荧光性质。     

基于一种柔性和角型有机芳香多酸配体的两种3D配位聚合物的合成、结构和荧光性

通过水热合成的方法制得具有三维超分子结构的2种配位聚合物{[Zn（L）（bpa）_0.5（H₂O）₂]·2.25H₂O}_n（1）和{[Cd（L）（H₂O）]·2H₂O}_n（2）,其中,H₃LCl为氯化5-（4-羟基吡啶基甲基）间苯二甲酸,bpa为1,2-二（4-吡啶基）乙烷。这2种化合物的结构通过单晶X射线衍射、红外光谱（IR）、元素分析、热重分析（TG）等方法进行了表征。结构解析表明：化合物1是一种梯型链式结构,并通过链间氢键作用延伸成了3D超分子网络;化合物2为含有大量一维隧道空腔的2D配位网络。此外,研究了这2种化合物的荧光性质。     

间苯二甲酸连接的氢键导致的二维锌配位聚合物的合成及晶体结构

由于配位聚合物在催化材料,磁性材料和光学材料等领域内具有广泛的 应用价值,近年来人们已经合成了不少多维配位聚合物,并对其进行了结构鉴定和性质研究。配位聚合物一般都是通过体系内的配位键、氢键,和金属－金属间相互作用等作用力形成。在大多数的体系中,一般采用含氮基团,如4,4－联吡啶,2,4,6－三（4－吡啶基）－1,3,5－三嗪,1,4－二咪唑丁胺等作为桥连配体合成具有各种不同拓扑结构的无限伸展体系。同时,利用含氧基团作为桥基合成各类配位聚合物也是一个重要的途径,一般为多酸体系,如1,3,5－三苯甲酸,马来酸等。我们通过分子自组装作用,合成了一例由间苯二甲酸作桥基通过氢键导致的金属锌的二维配位聚合物,通过单晶X－射线衍射,研究了它的结构。     

DAIP树脂及其复合材料的性能研究

加入热固性丁苯树脂可降低DAIP树脂的酯键密度,提高其耐水性,在该体系中加入适量的偶联剂,可改善树脂与玻璃纤维的界面,提高复合材料的耐水性和介电性能。