新颖孤立的金属环组装而成的三维氢键超分子化合物的合成及晶体结构

A novel discrete dinuclear metaUacyclic copper（Ⅱ） complex, [Cu2L2（H2O）2]·3H2O （1） has been firstly prepared where L is derived from the 1 ; 2 condensation of 2,2＇-bipyridyl-3,3＇-diformylhydrazide and acetone during the formation of the complex. Single-crystal X-ray diffraction analysis determines that the complex consists of dinuclear metallacyclic units [Cu2L2（H2O）2] where two metal centers are linked together through two bis（chelating） bridge ligands L to form a bizarre cavity with size 0.9417 nm× 0.4999 nm× 0.6930 nm. Interestingly, the metal coordination also creates hydrogen bond sites that further aggregate these metallacycles into a 3D supramolecular structure with 2D perpendicular hydrophilic tunnels in crystal.     

一维链状超分子化合物[Zn(dafo)2(H2O)2](NO3)2(dafo=4,5-二氮芴-9-酮)的合成、表征和晶体结构

超分子化学是分子间弱相互作用和分子组装的化学,近年来超分子晶体日益受到重视,超分子化合物在材料,催化,药物等领域有广泛的应用前景[1,2]。4,5鄄二氮芴鄄9鄄酮(dafo)是一种多吡啶配体,它含有羰基,易衍生出各种桥联配体,该化合物及其衍生物有特殊的结构和性能[3~5]。Dafo具有     

一维链状超分子化合物[Zn(dafo)2(H2O)2](NO3)2(dafo=4，5-二氮芴-9-酮)的合成、表征和晶体结构

A novel one-dimensional chain complex [Zn(dafo)₂(H₂O)₂](NO₃)₂ was synthesized. It has been characterized by IR, UV, TGA, Elemental analysis and X-ray diffraction analysis. The crystal belongs to triclinic system, P1 space group. The Crystallographic data are: a= 0.702 7(14) nm, b= 0.828 95(17) nm, c= 10.225(2) nm, α = 95.02(3)°, β = 91.45(3)°, γ = 99.85(3)°. The crystal structure data indicate that the Zn(Ⅱ) ion was coordinated with the four nitrogen atoms of two dafo and two oxygen atoms of two coordination water molecules, respectively. The complex has a one-dimensional chain structure, which is formed by hydrogen bonds.     

含4,4'-联吡啶桥联的阳离子链和嘌呤-羧酸根抗衡阴离子的一维FeⅡ和CoⅡ聚合物,及由混合羧酸根配体构筑的二维EuⅢ聚合物的合成与表征

通过2′,3′-双脱氧肌苷和氯乙酸反应,得到1个多功能配体2-(6-oxo-6,9-dihydro-1H-purin-1-yl)acetic acid(HL)。该配体与其它附加配体一起与相应的金属盐反应,分别得到3个配位聚合物{[Fe(4,4′-bpy)(H2O)4](L′)2}n(1),{[Co(4,4′-bpy)(H2O)4](L′)2}n(2)和{[Eu(ox)0.5(su)(H2O)2]·H2O}n(3)(4,4′-bpy=4,4′-二联吡啶,ox=草酸盐,su=琥珀酸盐,L′=L的互变异构体2-(6-oxo-6,7-dihydro-1Hpurin-1-yl)acetate]。3个配合物均为单斜晶系C2/c空间群。配合物1和2为异质同构体,是由4,4′-二联吡啶桥联金属离子形成的一维链状结构,配合物3是由混合羧酸根构筑的二维框架结构。在配合物1和2中,脱质子的配体HL没有与金属离子配位,而是以互变异构体L′并通过氢键结合成二聚阴离子对[(L′)]2作为抗衡离子存在于配合物中。在配合物3中,配体HL分解为草酸根,2个EuⅢ被草酸根连接成二聚单元,这个二聚单元又被琥珀酸根连接成二维聚合物。另外还对配合物1和2的红外光谱、热分解性质以及配合物3的荧光性质进行了分析研究。     

二茂铁丙烯酸和2,2‘—联吡啶的混配合物的合成与表征

合成了二茂铁丙烯酸和２,２‘－联吡啶与Ｚｎ,Ｃｄ,Ｈｇ,及Ｐｂ的混配合物,用元素分析,ＩＲ,ＵＶ,＾１ＨＮＭＲ,摩尔电导和热分析确定了这些配合物的组成为：（Ｃ５Ｈ５ＦｅＣ５Ｈ４ＣＨ＝ＣＨＣＯＯ）２Ｍ（Ｃ５Ｈ４Ｎ）２.     

新型三维间排层状钴磷酸盐配合物Co3(PO4)2·6H2O的合成与晶体结构

A new three dimensional layered cobalt phosphate complex Co₃(PO₄)₂·6H₂O, was prepared by hydro-thermal reaction of Co(CH₃COO)₂·4H₂O and H₃PO₄, NH₄VO₃. The crystal structure of the complex was deter-mined by single-crystal X-ray diffraction. The result indicates that it crystallizes in the tetragonal space group I4/m. It rarely occurs in cobalt phosphate complex to form two kinds of coordinate geometry of Co(Ⅱ), six water molecular oxygen atoms surround Co(Ⅰ) and form an octahedron geometry, Co(2) bond to four oxygen atoms from 4PO₄^3- and one water molecular oxygen and build a tetragonal pyramid. The kinetic study shows that the first decomposition stage is governed by A(?)B(?)C mode. CSD: 414600.     

配位聚合物[Ni(Hsal)2(Py)2]n(Hsal=水杨酸根,Py=吡啶)的合成,表征和晶体结构

用水杨酸和吡啶与Ni(ClO4)26H2O 合成了一个新颖配位聚合物[Ni(Hsal)2(Py)2]n。对配合物进行了X射线衍射结构表征, C24H20N2NiO6, Mr = 491.13, 晶体属三斜晶系, P 空间群, 晶胞参数: a = 7.372(2), b =10.852(2), c = 14.728(3) ? a = 108.36(3), b = 93.83(3), g = 103.67(3), V = 1073.7(4) ?。F(000) = 508, m = 0.949mm-1, Z = 2, Dc = 1.519 g/cm3。最后修正到R = 0.0390, wR = 0.0772。配合物中Ni为五配位, 呈四方锥构型。配合物中2个水杨酸根的配位方式不一样, 其中一个水杨酸根作为双齿桥连配体, 使配合物呈一维链状结构。水杨酸苯环的-堆积作用和分子间的氢键作用, 又使配合物呈二维网络结构。     

含液晶基元的1,3,4-噻二唑衍生物的合成与表征

制备了3个含液晶基元的1,3,4-噻二唑衍生物,并用元素分析、核磁(NMR)、红外光谱(IR)对它们的结构进行了确认.其液晶性能和热行为则采用偏光显微镜(POM)、差示扫描量热仪(DSC)及热重分析仪(TG)进行了表征,研究结果表明所制备的化合物均可显示液晶性,其中化合物C4具有良好的液晶性能和较宽的液晶范围.热分解测试显示随着烷基链上碳原子的增加,化合物的分解温度逐渐降低.     

2-甲基-1H-咪唑-4,5-二羧酸及其钴(Ⅱ)配合物的合成、结构和性能研究

以邻苯二胺和丙二酸为原料,通过缩合、氧化反应合成新型咪唑羧酸配体2-甲基-1H-咪唑-4,5-二羧酸(L).用NaOH调节体系的pH值为8.0左右,配体L和CoSO4.6H2O在水热条件下反应生成配合物[C(o L)(2 H2O)2](1).配合物1属于正交晶系Pbca空间群.在该化合物中,C(o Ⅱ)离子采取稍微扭曲的八面体配位构型,两个配体L以脱质子的羧基O原子和咪唑环上紧邻的N原子从赤道平面与Co(II)离子螯合配位,而两个水分子则占据轴向位置配位.有趣的是:合成的配合物1具有多重氢键连接点,是优异的氢键合成子,通过复杂的N—H···O和O—H...O氢键组装成三维的超分子化合物.进一步的热化学研究表明,该化合物相当稳定,在空气氛围下升温到200℃以上才开始分解.