【作者】 王贤文；

【导师】 梁宏； 陈振锋；

【作者基本信息】 广西师范大学 ， 无机化学， 2004， 硕士

【摘要】 一、 合成了两个以药物喹碘仿为桥联配体的中性一维配位聚合物。水热(溶剂热)条件下药物喹碘仿与Co(ClO4)2·6H2O、ZnClO4·6H2O自组装得两个中性一维配位聚合物：[C9H10IN3O4SZn]n (1)，[C14H12CoIN2O6S] n (2)。X-射线衍射分析结果表明化合物1的空间群为 P21/n，化合物2的空间群为P21/c，其中化合物 1为五配位的三角双锥几何构型，化合物2为六配位的八面体配位方式。化合物 1通过喹碘仿桥联成一维无限链状聚合物；配合物2中两分子去质子的喹碘仿以旋转倒反的配位形式与两个钴(II)配位，形成一个笼形的二聚体，二聚体单元通过4,4-联吡啶桥联成一维聚合物。两个化合物中都存在丰富的氢键，通过氢键连接成三维网状结构。二、 合成了两个新颖的二维层状配位聚合物。 药物喹碘仿与MnCl2·4H2O、Co(ClO4)2·6H2O在水热(溶剂热)条件下反应得两个配位聚合物：[C9H9NO6SMn] 2n (3)，[C9H9NO6SCo] 2n (4)。X-射线衍射分析结果表明化合物 3和化合物 4具有相似的结构，均属于正交晶系，空间群Pbca。金属中心为六配位略微变形的八面体几何构型。配体喹碘仿中的碘原子在反应过程中已离去，化合物通过去质子的8-羟基喹啉-5-磺酸桥联成中性二维层状配位聚合物。化合物3、4通过分子间氢键连接成三维超分子结构。磁性实验表明化合物3中Mn(II)原子间表现出铁磁性，化合物4中Co(II)原子间表现出反铁磁性。三、 合成了稀土Gd(III) 、Er(III)新颖配位聚合物。 药物喹碘仿分别与Gd(ClO4)3·6H2O、Er(ClO4)3·6H2O在水热(溶剂热)条件下自组装得两个配合物：<WP=3>[C24H33GdN3O16S2] n (5)、[C18H13ErI2N2O10S2]2 n (6)， X-射线衍射分析结果表明化合物5、6具有相同的空间群P-1，均为八配位的四方反棱柱的几何构型。在化合物5中4,4-联吡啶中的两个氮原子在反应过程中已甲基化；喹碘仿中的碘原子已离去；两分子去质子的8-羟基喹啉-5-磺酸以旋转倒反的配位形式与两个Gd(III)配位形成一个笼形的二聚体；化合物通过去质子的8-羟基喹啉-5-磺酸桥联成阴离子型的一维配位聚合物。化合物6中，磺酸基以二齿配位形式与Er(III)配位，两个磺酸基氧原子把相邻的两个金属铒离子连接起来形成双核金属构筑块，两个旋转倒置的配体和两个金属铒原子形成一个笼形的二聚体，由双核金属构筑块和笼形的二聚体无限连接成二维配位聚合物结构。两个化合物中均存在丰富的氢键，通过氢键连接成三维超分子结构。四、 合成了两个二聚体的双核配合物。 喹碘仿分别与Cu(NO3)2·3H2O、Zn(Ac)2·2H2O在水热(溶剂热)条件下反应得两个配合物：[C18H20Cu2I2N2O14S2] (7)、[C18H22I2N2 O15S2Zn2] (8) 。化合物7为双核金属二聚体，两分子去质子的喹碘仿以旋转倒反的配位形式与两个铜(II)配位，铜原子采取五配位的四方锥几何构型。化合物8 为两个独立的双核金属二聚体，两分子去质子的喹碘仿以旋转倒反的配位形式与两个锌(II)配位，锌原子的配位数为六，几何构型为八面体。通过氢键连接两个化合物都成三维网状结构。五、合成希夫碱吡啶-2-甲醛缩2-氨基苯骈噻唑Cu(I)配合物及设计合成吡啶类中性桥联配体希夫碱吡啶-3-甲醛缩4-氨基安替比林(简称L3)。设计合成吡啶类中性桥联配体希夫碱吡啶-3-甲醛缩4-氨基安替比林：[C17 H16 N4 O] (9)。合成希夫碱吡啶-2-甲醛缩2-氨基苯骈噻唑(简称ABTP)并在溶剂热条件下首次获得2-氨基苯骈噻唑类希夫碱配合物的晶体：[Cu(ABTP)(PPh3)2]ClO4 (10)。X-射线衍射分析结果表明化合物10属三斜晶系，空间群为P-1，金属中心Cu(I)采用四配位的变形四面体几何构型。六、合成了两个以吡啶-3-甲醛缩4-氨基安替比林为桥联配体的中性二维分子箱。 配体吡啶-3-甲醛缩4-氨基安替比林与MCl2·4H2O(M=Mn,Fe)在溶剂热条件下自组装得两个二维分子箱化合物：[Mn(μ2-Cl)(L3)C1] 2n (11) 、[Fe(μ2-Cl)(L3)C1] 2n (12)。<WP=4>X-射线衍射分析结果表明这两个化合物具有相同的空间群P21/n，都属于三斜晶系。化合物均为五配位，空间构型为四面体。两个金属原子被两个Cl原子桥连成金属二聚体M2Cl2的形式，相邻的金属二聚体M2Cl2通过中性桥联配体L3连接形成了二维长方形的分子方框。两个化合物都具有较大的空穴。磁性质实验表明化合物11中Mn(II)原子间表现为反铁磁相互作用，化合物12中Fe(II)原子间有铁磁相互作用。七、合成了希夫碱3-吡啶甲醛缩4-氨基安替比林Zn(II)一维配位聚合物及Co(II)二聚体配合物。吡啶-3-甲醛缩4-氨基安替比林(简称L3)分别与ZnCl2·4H2O、Co(NO3)2·6H2O在溶剂热条件下合成化合物：[Zn2Cl4(L3)2] n (13)、[Co(L3)2(NO3)2]2 (14)。X-射线衍射分析结果表明化合物13为一维配位聚合物，化合物14为二聚体的双核结构。两个化合物均属于三斜晶系，空间群均为 P-1。化合物13的中心金属锌原子为四配位，采取四面体的空间构型；化合物14的中心钴原子为六配位，采取八面体的空间几何构型。八、 合成了三个希夫碱吡啶-4-甲醛缩4-氨基安替比林M(II)（M=Fe、Co、Ni）配合物。配体吡啶-4-甲醛缩4-氨基安替比林(简称L4)分别与M(II)(M=Fe、Co、Ni)的金属盐在溶剂热条件下反应得三个化合物：[Fe(L4)2(Cl2)(H2O)] (15)?更多还原

【Abstract】 I. Two neutral one-dimensional coordination polymers bridged by drug Chiniofon. [C9H10IN3O4SZn]n (1),[C14H12CoIN2O6S] n (2) were assembled under hydro(solv)thermal conditions between the drug chiniofon with Co(ClO4)2·6H2O and ZnClO4·6H2O respectively. The results of X-ray crystallographic analysis indicate that in complex 1 the central zinc atom is five-coordinated with triangle bipyramid geometry and P21/n space group; and the central cobalt atom is six-coordinated with octahedron geometry and P21/c space group in compound 2.One-Dimensional infinite-chain of complex 1 formed through chiniofon linking.In complex 2 two deprotonated inversion-related chiniofon ligands and two Co(II) atoms form a cage-like dimer and the cage-like dimer is bidged by 4,4-bpy to generate one-dimensional coordination polymer. There are abuntant hydrogen bonds in two complexes, and three-dimensional networks are formed through hydrogen bonds. II. Two nevol 2D layered coordination polymers. [C9H9NO6SMn]2n(3)，[C9H9NO6SCo]2n(4) were synthesized by hydro(solv)thermal treatments between the drug chiniofon with MnCl2·4H2O and Co(ClO4)2·6H2O respectively. The results of X-ray crystallographic analysis indicate that the two complexes are isomorphous and belong to Orthorhombic crystal system with Pbca space group.The central metals was six-coordinated with octahedron geometry. The Iodin atom of chiniofon have been removed and neutral two-dimensional layered coordination polymers are formed through deprotonated 8-hydroxylquinoline-5-sulfonic acid ligand bridging.The supramolecular structures are generated through intermolecular hydrogen bonds. <WP=6>Variable temperature magnetic susceptibility measurements reveal that the presence of a ferromagnetic interaction between the Mn(II) centers in complex 3 and the presence of an antiferromagnetic interaction between the Fe(II) centers in complex 4.III. The novel rare earth Gd(III),Er(III) coordination polymers. [C24H33GdN3O16S2]n(5),[C18H13ErI2N2O10S2]2n(6) were assembled under hydro(solv) thermal conditions between the drug chiniofon with Gd(ClO4)3·6H2O and Er(ClO4)3·6H2O respectively. The results of X-ray crystallographic analysis indicate that the two complexes have same space group P-1. The central metals of two complexes are eight-coordinated with capped square antiprism geometry. The pyridine N atoms of 4,4-bpy have been attached by methyls in complex 5; the Iodin atom of chiniofon has been removed;and the deprotonated inversion-related 8-hydroxylquinoline-5-sulfonic acid ligands and two Gd(III) atoms form a cage-like dimer and the anionic one-dimensional structure is formed through the deprotonated 8-hydroxylquinoline-5-sulfonic acid ligand bridging.In complex 6,the sulfonic group acts as bidentate ligand through its two O atoms linking two adjacent Er(III) ions to form dinuclear building block and two inversion-related chiniofon ligands and two Er(III) atoms form a cage-like dimer; the two-dimensional coordination polymer is generated through such dimers and cage-like dimers infinitely linking. There exist abuntant hydrogen bonds in two complexes and three-dimensional supramolecular structure formed through hydrogen bonds bounding.IV. Two dinuclear dimer compouds. [C18H20Cu2I2N2O14S2] (7) and [C18H22I2N2 O15S2Zn2] (8) were synthesized by hydro(solv)thermal treatments between the drug chiniofon with Cu(NO3)2·3H2O and Zn(Ac)2·2H2O respectively. The results of X-ray crystallographic analysis indicate that in complex 7 Cu atoms is five-coordinated with square pyramid geometry, and two deprotonated inversion-related chiniofon ligands and two Cu(II) atoms form a cage-like dimer. The complex 8 is two independent dimers; two deprotonated inversion-related chiniofon ligands coordinate to <WP=7>two Zinc atoms forming a cage-like dimer; the Zinc atoms are six-coordinated with octahedron geometry. Three-dimensional structure are formed through hydrogen bonds interaction.V. Synthesis of Schiff base derived from pyridine-2-carboxaldehyde and 2-aminobenzothiazole and its Cu(I更多还原