【作者】 肖冬荣；

【导师】 王恩波；

【作者基本信息】 东北师范大学 ， 无机化学， 2007， 博士

【摘要】 本论文致力于利用不同类型的V-型配体,有机药物和有机含N配体,与多核金属-氧簇和金属离子构筑新型的螺旋配合物,研究这类化合物的合成条件及规律,探讨V-型配体和螯合含N配体对螺旋结构形成的影响,研究分子自组装原理,探索新物质结构和性能间的关系。利用水热技术,合成了一系列新型的螺旋配合物,通过元素分析,IR,EPR,XPS,XRPD,TG和单晶X-射线衍射对晶体结构进行了表征,对化合物的热稳定性、磁学特性和荧光性质进行了初步研究。1.以多金属钒氧簇为建筑单元,通过引入{MxLy}（M =过渡金属离子,L =含N螯合配体）片段,水热合成和结构表征了6种新型的螺旋多酸配合物: Cu（phen）V₂TeO₈ （1） Ni（phen）V₂TeO₈ （2） [V₄O₇（HAsO₄）₂（phen）₂] （3） [{CoIII（phen）₂}2V₈O₂₃] （4） [Co（2,2’-bpy）₂V₃O_8.5] （5） [{Zn（2,2’-bpy）}₂V₈O₂₁] （6）化合物1和2含有两种不同类型的螺旋,是第一个由金属-有机配合物亚单元修饰的碲钒酸盐,也代表了第一个具有手性层结构的有机无机杂化碲钒酸盐。化合物3是第一个有机氮配体直接配位在二维{V/As/O}无机物层上的化合物,同时也是第一个具有螺旋特征的有机无机杂化砷钒酸盐。化合物4～6是三个具有新颖层状结构的有机-无机杂化钒酸盐化合物,并且它们的结构中都含有左手和右手的螺旋链。通过考察化合物1-6的结构,我们相信L和{MxLy}片段对于螺旋结构的形成是非常重要的。此外,对化合物1,2和4进行了磁学性质的研究。2.利用金属离子或由其构成的多核金属簇为建筑单元,通过引入V型的二苯甲酮四羧酸（bptc）和线性的4,4′-联吡啶（bpy）配体,借助水热合成技术合成并表征了9个柱撑螺旋层配位聚合物: [Cu₂（bptc）（bpy）₂] （7） [Fe₃（Hbptc）₂（bpy）₃（H₂O）4]·2H₂O （8） [Ni₃（Hbptc）₂（bpy）₃（H₂O）4]·2H₂O （9） [Co₂（bptc）（bpy）（H₂O）]·0.5bpy （10） [Cd₂（bptc）（bpy）（H₂O）2]·H₂O （11）[Mn₂（bptc）（bpy）_1.5（H₂O）3] （12） [Mn₂（bptc）（bpy）_0.5（H₂O）5]·0.5bpy （13） [Mg₂（bptc）（bpy）_0.5（H₂O）5]·0.5bpy （14） [Co₂（bptc）（bpy）_0.5（H₂O）5]·0.5bpy （15）化合物7是一个含有四种不同螺旋的柱撑螺旋层配合物。化合物8和9是由具有螺旋特征的二维手臂式层,通过4,4′-联吡啶柱撑的三维配合物。化合物10是一个含有四种不同螺旋的柱撑螺旋双层配位聚合物。化合物11是一个具有纳米尺寸管状隧道的三维柱撑螺旋层配位骨架。化合物12的三维结构是由{Mn（bptc）（H2O）}n2n-螺旋层和层间的[Mn2（bpy）3（H2O）4]4+复合物柱子共价连结形成的。化合物13～15显示出一种新颖的螺旋双层结构。它们的三维超分子结构与化合物12的三维结构相似。因此,化合物13～15的三维超分子结构也可以看作是由一个二维氢键层通过金属-有机复合物柱撑而形成的。这些化合物同时拥有柱撑和螺旋结构的优点,很好地架接起柱撑结构和螺旋结构之间的联系。此外,对上述化合物进行了荧光和磁学性质的研究。3.利用双核金属簇和单核金属离子为节点,通过引入长V型羧酸配体和线性的4,4′-联吡啶配体,成功合成了2个空前的自穿网络。{[Zn₄（bptc）₂（bpy）₄]·（C₅H₃N）·4H₂O}n （16） {[Cd₂（sdba）₂（bpy）（H₂O）₂]·2H₂O}n （17）化合物16是一个含有五股分子辫,九重交织meso-螺旋和17重交织螺旋的三维自穿网络。其中的五股分子辫是目前最高股数的分子辫。化合物17是一个罕见二维自穿网络,并且含有pseudo-Borromean环和双股螺旋。如果考虑化合物17中层间强氢键,化合物17是一个空前的三维八连结的自穿网络（421.67）,是目前自穿体系中最高连结拓扑。此外,对两个化合物进行了荧光性质的研究。4.利用金属离子或由其构成的多核金属簇为建筑单元,通过引入环丙沙星（cfH）和芳环多羧酸配体,水热合成和结构表征了一系列新型的螺旋金属-药物配合物: [Zn（cfH）（Hbtc）]·H2O （18） [Zn₂（cfH）2（odpa）] （19） [Zn₂（cfH）2（bptc）]·4H₂O （20） [Ca（cfH）₂（1,2-Hbdc）₂]·2H₂O （21） [Mn（cf）₂]·2.5H₂O （22） [Co（cf）₂]·2.5H₂O （23） [Zn（cf）₂]·2.5H₂O （24） [Cd（cf）₂]·2.5H₂O （25） [Mg（cf）₂]·2.5H₂O （26） [Ba₂（cf）₂（1,4-bdc）（H₂O）₂]·H₂O （27） [Sr₆（cf）₆（1,4-bdc）₃（H₂O）₆]·2H₂O （28）[Mn₂（cfH）₂（bptc）（H₂O）₂]·8H₂O （29） [Cd₂（cfH）₂（bptc）（H₂O）₂]·8H₂O （30） [Mn（cfH）（1,3-bdc）] （31） [Co（cfH）（1,3-bdc）] （32） [Zn（cfH）（1,3-bdc）] （33） [Zn2（cfH）₄（1,4-bdc）]（1,4-bdc）·13H₂O （34）化合物18是一个含有五种不同螺旋的金属-环丙沙星配合物。化合物19含有三种不同螺旋,是第一个具有二维手性层结构的金属-喹诺酮配合物。化合物20具有和化合物19相似的手性层结构。化合物21的超分子结构中含有左手和右手的氢键螺旋。化合物22²6显示出一种新颖的二维格子层,该层中存在左手和右手的单股螺旋。化合物27和28是两个含有多核碱土金属簇的二维手臂式层状金属-环丙沙星配合物。化合物29和30是由[M2（cfH）₂（H2O）₂]双核单元和bptc配体连接而形成的一维链状结构。化合物31³3是由[M2（cfH）₂（CO2）₂]双核单元和过1,3-bdc配体连接而形成一维双链结构。化合物34是由一对[Zn（cfH）₂]²⁺片断通过1,4-bdc配体桥连形成的双核哑铃型分子。这些化合物的合成将为我们进一步理解喹诺酮抗菌药的活性机理提供新的结构信息。此外,研究了由d10金属构筑的金属-环丙沙星配合物的荧光性质和化合物22,23,29和31的磁学性质。更多还原

【Abstract】 The aim of this thesis is to synthesize new helical coordination compounds on the basis of V-shaped ligands, organic drugs, organic N-donor ligands and multi-nuclear metal-oxygen clusters or metal ions, to study the synthetic conditions and rules for these compounds, analysis influence of V-shaped ligands and N-donor chelate ligands on the formation of helical structure, and to explore the relationships between structures and properties for these new compounds.A series of new helical coordination compounds have been synthesized on the basis of hydrothermal technique and structurally characterized by elemental analyses, IR, EPR, XPS, XRPD, TG and single crystal X-ray diffractions. The thermal stabilities, magnetic properties and fluorescent activity of these compounds have been studied.1. Six new helical polyoxometalates have been hydrothermally synthesized on the basis of polyoxovanadates decorated or connected by {MxLy} （M = transition metal ions,L = N-donor chelate ligands） fragments: Cu（phen）V₂TeO₈ （1） Ni（phen）V₂TeO₈ （2） [V₄O₇（HAsO₄）₂（phen）₂] （3） [{CoIII（phen）₂}2V₈O₂₃] （4） [Co（2,2’-bpy）₂V₃O_8.5] （5） [{Zn（2,2’-bpy）}₂V₈O₂₁] （6）Compounds 1 and 2 exhibit a novel 2D chiral layer structure featuring two distinct helices. Compounds 1 and 2 represent the first vanadium tellurites covalently bonded with the metal-organic complex moieties and the two compounds also represent the first example of organic-inorganic hybrid vanadium tellurites containing chiral layer structure. Compound 3 represents the first example of 2D inorganic vanadium arsenate backbone decorated with the directly coordinated organic ligands and the compound also represents the first example of organic-inorganic hybrid vanadium arsenate with helical characters. Compounds 4-6 are three novel 2D inorganic-organic hybrid vanadate complexes containing left-handed and right-handed helical chains. Furthermore, by inspection of the structures of 1-6, it is believed that the L and {MxLy} fragments are important for the formation of the helical structures. In addition, the magnetic properties of compounds 1, 2, and 4 were also investigated.2. Nine new pillared helical-layer coordination polymers have been hydrothermally synthesized on the basis of metal ions or their multi-nuclear clusters connected by V-shaped 3,3’,4,4’-benzophenonetetracarboxylate （bptc） and linear 4,4’-bipyridine （bpy） ligands: [Cu₂（bptc）（bpy）₂] （7） [Fe₃（Hbptc）₂（bpy）₃（H₂O）4]·2H₂O （8） [Ni₃（Hbptc）₂（bpy）₃（H₂O）4]·2H₂O （9） [Co₂（bptc）（bpy）（H₂O）]·0.5bpy （10） [Cd₂（bptc）（bpy）（H₂O）2]·H₂O （11） [Cu₂（bptc）（bpy）₂] （7） [Fe₃（Hbptc）₂（bpy）₃（H₂O）4]·2H₂O （8） [Ni₃（Hbptc）₂（bpy）₃（H₂O）4]·2H₂O （9） [Co₂（bptc）（bpy）（H₂O）]·0.5bpy （10） [Cd₂（bptc）（bpy）（H₂O）2]·H₂O （11）Compound 7 is a pillared helical-layer complex featuring four distinct helical chains. Compounds 8 and 9 are isostructural and feature 3D structures formed from the interconnection of arm-shaped helical layers with bpy pillars. Compound 10 is a pillared helical-double-layer complex containing four different types of helices. Compound 11 exhibits a novel 3D covalent framework featuring nanosized tubular channels that are built from helical layers pillared by bptc ligands. The structure of 12 is constructed from {Mn（bptc）（H2O）}n2n- layers, which consist of left- and right-handed helical chains, pillared by [Mn2（bpy）3（H2O）4]4+ complexes into a 3D framework. Compounds 13-15 exhibit interesting 2D helical-double-layer structures. Furthermore, the 3D supramolecular structures of 13-15 are similar to the 3D structure of 12. Therefore, the 3D supramolecular structures of 13-15 can also be considered as being constructed from 2D hydrogen-bonded layers, which consist of {M（bptc）（H2O）2}n2n- ribbons, pillared by [M2（bpy）（H2O）6]4+ complexes. These compounds combine respective merits of pillared-layer and helical structures, which may provide a bridge between pillared-layer and helical systems. In addition, photoluminecent and magnetic properties of these compounds are studied.3. Two self-penetrating networks have been constructed based on binuclear or mononuclear metals as nodes and long V-shaped ligands and linear bpy ligands as links. {[Zn₄（bptc）₂（bpy）₄]·（C₅H₃N）·4H₂O}n （16） {[Cd₂（sdba）₂（bpy）（H₂O）₂]·2H₂O}n （17）Compound 16 adopts a novel 3D framework containing quintuple-stranded molecular braid, 9-fold meso helices and 17-fold interwoven helices, among which the quintuple-stranded molecular braid represents the highest-stranded molecular braid known in the field of coordination polymers and inorganic compounds. Compound 17 is an uncommon self-penetrating 2D network containing pseudo-Borromean links and double-stranded helices. More interestingly, when the strong hydrogen bonds between layers are taken into account, the resulting net of 17 becomes an 8-connected 3D self-penetrating network with an unprecedented （421.67） topology, which represents the highest connected topology presently known in self-penetrating systems. Furthermore, the photoluminescent properties of two compounds were studied.4. A series of new helical metal-drug complexes have been hydrothermally synthesized on the basis of metal ions or their multi-nuclear clusters connected by aromatic polycarboxylate ligands and ciprofloxacin （cfH）: [Zn（cfH）（Hbtc）]·H2O （18） [Zn₂（cfH）2（odpa）] （19） [Zn₂（cfH）2（bptc）]·4H₂O （20） [Ca（cfH）₂（1,2-Hbdc）₂]·2H₂O （21） [Mn（cf）₂]·2.5H₂O （22） [Co（cf）₂]·2.5H₂O （23） [Zn（cf）₂]·2.5H₂O （24） [Cd（cf）₂]·2.5H₂O （25） [Mg（cf）₂]·2.5H₂O （26） [Ba₂（cf）₂（1,4-bdc）（H₂O）₂]·H₂O （27） [Sr₆（cf）₆（1,4-bdc）₃（H₂O）₆]·2H₂O （28） [Mn₂（cfH）₂（bptc）（H₂O）₂]·8H₂O （29） [Cd₂（cfH）₂（bptc）（H₂O）₂]·8H₂O （30） [Mn（cfH）（1,3-bdc）] （31） [Co（cfH）（1,3-bdc）] （32） [Zn（cfH）（1,3-bdc）] （33） [Zn₂（cfH）₄（1,4-bdc）]（1,4-bdc）·13H₂O （34）Compound 18 is a unique helical metal-cfH complex containing five types of helices. Compound 19 exhibits a novel 2D chiral layer structure featuring three distinct helices, and the compound represents the first example of metal-quinolone complexes containing chiral layer structure. The chiral layer structure of 20 is similar to that of 19. The supramolecular structure of 21 contains left-handed and right-handed hydrogen-bonded helice. Compounds 22-26 exhibit interesting two-dimensional rhombic grids featuring left-handed and right-handed single helice. The structures of 27 and 28 consist of unique two-dimensional arm-shaped layers based on the one-dimensional Ba-O-Ba chains or hexanuclear strontium cluster units. Compounds 29 and 30 are isostructural and feature one-dimensional structures formed from the interconnection of [M2（cfH）2（H2O）2] dimers with bptc ligands. Compounds 31-33 contain double-chain-like ribbons constructed from [M2（cfH）2（CO2）2] dimers and 1,3-bdc. Compound 34 consists of a pair of [Zn（cfH）2]2+ fragments bridged by a 1,4-bdc into a dinuclear dumbbell structure. The successful isolation of these compounds provides new structural information that will aid in understanding the mechanisms of action of the quinolone antibacterial drugs. The fluorescent study on the compounds based on d10 metals and the magnetic properties of compounds 22,23,29 and 31 are also discussed.更多还原