【作者】 钱保华；

【导师】 陆路德；

【作者基本信息】 南京理工大学 ， 应用化学， 2009， 博士

【摘要】 利用多羧酸及多膦酸合成结构独特的金属-有机骨架材料是杂化金属-有机配合物研究的主要方向。然而,由于磺酸根与过渡金属离子的弱配位能力使得过渡金属的芳香磺酸配合物的研究较少。同时,过渡金属离子与咪唑及有机多胺形成的配合物由于其独特的生物活性及优良的催化性能也受到了人们的广泛关注。本文主要研究了芳香二磺酸及有机多胺分别与过渡金属离子的配位行为,探讨合成新型过渡金属芳香磺酸及有机多胺配合物的方法、结构与表征。（1）利用1,5-萘二磺酸分别与氧化锌、氧化镉和碳酸锰在水溶液中反应后再与咪唑反应合成得到了三个新型结构的过渡金属配位聚合物:{[Zn（1,5-nds）（Him）₂（H₂O）]·2H₂O}_n（1）,{[Cd₂（1,5-nds）₂（Him）₄（H₂O）₂]·4H₂O}_n（2）和[Mn（1,5-nds,）（Him）₄]_n（3）。晶体结构分析表明,配合物1和2具有相似的二维层状结构。1,5-萘二磺酸根离子中的-SO₃基团以二种桥联方式进行配位;其一是与Zn原子以双齿配位,桥联的相邻Zn…Zn之间的距离为0.54523（16）nm（在配合物2中Cd…Cd之间是0.54533（9）nm）,整个1,5-萘二磺酸根作为μ₄桥联配体形成一维双核链状结构,沿链方向相邻Zn…Zn之间的最近距离为1.02530（22）nm（在配合物2中Cd…Cd之间是1.02570（11）nm）;另一类-SO₃^-基团是以单齿配位桥联,整个1,5-萘二磺酸根作为μ₂桥联配体,使链与链间相互联接形成二维聚合物结构,链间桥联Zn…Zn之间的距离为0.8017（2）nm（在配合物2中Cd…Cd之间是0.80194（22）nm）。再通过层间水分子与-SO₃^-基团的氢键作用使二维配聚物形成三维堆积结构。配合物3中Mn（Ⅱ）离子是畸变的八面体配位结构,1,5-萘二磺酸根以μ₂桥联方式配位,使相邻的[Mn（Him）₄]²⁺离子配位单元联接成一维链状聚合物。沿链方向Mn…Mn之间的最近距离为1.14499（12）nm。咪唑配体的引入有利于磺酸基团与Zn（Ⅱ）、Cd（Ⅱ）和Mn（Ⅱ）的配位,增强了磺酸基团的配位能力。运用Gaussian 03W和MOPAC 2007程序包分别对配合物1-3进行了单点能、电荷分布、键级及前线轨道附近的轨道的能量和组成进行了理论计算,对配合物的形成从理论上提供佐证。通过红外光谱、元素分析、核磁共振氢谱及热重分析对其结构和性质进行了表征。（2）利用1,5-萘二磺酸分别与氢氧化铜和碳酸钴在水溶液中反应再与咪唑配体反应合成得到了二个新型结构的过渡金属配合物:[Cu（Him）₂（H₂O）₄]（1,5-nds）（4）和[Co（Him）₂（H₂O）₄]（1,5-nds）（5）;利用对甲苯磺酸锌的水溶液中引入邻苯二胺配体合成得到新型配合物[Zn（C₆H₈N₂）₃（H₂O）]（C₇H₇SO₃）₂·3H₂O（6）。配合物4和5具有相似的空间结构。在水溶液中存在咪唑时,1,5-荼二磺酸根离子没有与Cu（Ⅱ）和Co（Ⅱ）配位而仅作为对阴离子存在,但由于-SO₃^-基团与水分子及咪唑之间的氢键作用导致二维有机一无机层状结构的形成。配合物6中的对甲苯磺酸根离子中的磺酸基团也未参与配位。而是通过磺酸基团上氧原子的氢键作用使化合物晶体获得稳定结构。（3）以溶剂热法合成了新型配位聚合物[Zn（acac）₂（4,4’-bipy）]_n（7）。通过IR,¹HNMR,TGA和单晶X-射线衍射对其结构进行了表征。该配合物是由Zn²⁺与乙酰丙酮酸根离子组成的电中性平面单元再通过4,4’-bipy组装而成的一维链状结构。运用Gaussian 03W程序包对配合物7进行了单点能、电荷分布和前线轨道附近的轨道的能量和组成进行了理论计算。计算结果很好地佐证了配位环境。（4）合成了以有机多胺三（2-氨基乙基）胺与单羧酸配体（HCOO）桥联而成的新型双核锌配合物[（tren）Zn（HCOO）Zn（tren）]（BF₄）₃（8）、与氯混配的单核锌配合物[（tren）ZnCl]BF₄（9）及1,3-丙二胺（1,3-pn）与锌的单核配合物[Zn（1,2-pn）₃]（ClO₄）₂（10）。晶体结构分析表明:在配合物8和9中,每个Zn（Ⅱ）周围均呈畸变的三角双锥配位环境。而在配合物10中,每个Zn（Ⅱ）周围呈八面体结构配位环境。在配合物8的晶体中以配体tren的-NH2基团上的N原子与BF₄^-中的F原子之间的氢键作用,形成三维层状结构。（5）以有机多胺1-[二（2-氨基乙基）氨基]-2-丙醇为配体与过渡金属镍（Ⅱ）、镉（Ⅱ）和铜（Ⅱ）合成了三个新型配合物[Ni(C₇H₁₉N₃O)₂]（ClO₄）₂（11）,[Cd(C₇H₁₉N₃O)₂]（ClO₄）₂（12）,{[Cu₂(C₇H₁₉N₃O)₂(C₁₀H₈N₂)]（ClO₄）₄·H₂O)（13）。并通过元素分析、IR、¹HNMR及单晶X-射线衍射对化合物进行了表征。配合物11是六配位的单核结构,1-[二（2-氨基乙基）氨基]-2-丙醇配体中的羟基O原子未参与配位。配合物12是八配位的单核结构,与11不同的是1-[二（2-氨基乙基）氨基]-2-丙醇配体作为四齿配体参与配位。配合物12是以4,4’-联吡啶桥联配体中的1个N原子和多胺中的3个N原子及1个O原子与铜离子形成4N+O五配位畸变的四方锥构型,形成双核结构。[Cu₂(C₇H₁₉N₃O)₂(C₁₀H₈N₂)]⁴⁺中Cu…Cu间的距离为1.1122nm。以上结果表明,1-[二（2-氨基乙基）氨基]-2-丙醇配体具有配位模式多变的特点。通过差热和热重对三个配合物在氮气氛中的热分解性质进行了测定,结果发现:配合物11和13具有相似的热分解特性,即分别加热到298℃和260℃会发生爆炸分解的反应。结果说明该类化合物的热不稳定性,同时也为进一步研究该类化合物作为潜在的含能材料使用提供了有用的信息。更多还原

【Abstract】 Current efforts on hybrid metal-organic complexes are directed mostly toward synthesis of diverse metal-organic frameworks using polycarboxylates and phosphonates. However, a few of studies are dedicated to the metal arenesulfonates owing to the weak coordination ability of sulfonate toward transition metal ions. In addition, the transition metal complexes with imidazole and organic polyamines have received considerable attention in recent years because of their diverse biological activity and excellent catalytic properties. In this paper, we discuss mainly the syntheses and coordination behavior of transition metal cations toward arenedisulfonates and organic polyamines.（1） Three new polymeric complexes{[Zn（1,5-nds）（Him）₂（H₂O）]·2H₂O}_n （1）, {[Cd₂ （1,5-nds）₂（Him）₄（H₂O）₂]·4H₂O}_n （2） and [Mn（1,5-nds）（Him）₄]_N （3） were prepared by the reactions of 1,5- naphthalenedisulfonate （1,5-nds） with zinc oxide, cadmium oxide, manganese carbonate and imidazole in aqueous solution, respectively. X-ray diffraction analysis reveals that complex 1 and 2 have the similar two-dimensional layer network structures. In complex 1, the -SO₃^- groups of the 1,5-nds ligand have two different coordination modes, one bridges two Zn atoms in a bidentate fashion with the shortest Zn…Zn distance being 0.54523（16） nm （0.54533（9） nm for Cd…Cd in 2）, the ligand acts as aμ₄ bridge and links four symmetry-related Zn centers forming a linear chains with the shortest Zn…Zn distance between Zn atoms separated by a 1,5-nds ligand being 1.02530（22） nm（1.02570（11） nm for Cd…Cd in 2）, while the other coordinates to the Zn atom in a monodentate fashion, the ligand acts as aμ₂ bridge and links the adjacent chains giving rise to a 2-dimensional network with the shortest Zn…Zn distance 0.8017（2） nm （0.80194（22） nm for Cd…Cd in 2）. The overall structure can be described as stacking of 2-dimensional networks, held together by inter-layered hydrogen bonds between water molecules and SO₃^-groups. In complex 3, Mn（Ⅱ） ion is coordinated in a distorted octahedral geometry. The [Mn（Him）₄]²⁺ units are linked by 1,5-nds which act as bidentate bridging ligands, leading to the forming of a 1-D Zig-Zag chain coordination polymer with Mn…Mn distance 1.14499（12） nm. There are significant inter-string hydrogen bonded interactions. Therefore, the 1,5-nds ligands have much stronger coordination ability to Zn（Ⅱ）, Cd（Ⅱ） and Mn（Ⅱ） in aqueous solution by introducing imidazole ligand as auxiliaries to these metal centers. The theoretical investigation of the complexes 1-3 as a structure unit were carried out with Gaussian 03W and MOPAC 2007 program packages, and the single-point energy, atomic charges distribution, bond order and composition of some frontier molecular orbitals were also discussed. Their properties were also characterized by element analysis, IR,¹H NMR and TG analysis.（2） Complexes [Cu（Him）₂（H₂O）₄]（1,5-nds） （4）, [Co（Him）₂（H₂O）₄]（1,5-nds） （5） and [Zn （C₆H₈N₂）₃（H₂O）]（C₇H₇SO₃）₂·3H₂O （6） hvae been synthesized and characterized by elemental analysis, IR , ¹H NMR spectroscopies, and X-ray single-crystal diffraction analysis. The complexes 4 and 5 own the same structure type. There is no direct coordination between SO₃^-and Cu²⁺ and Co²⁺ in the presence of water molecules and imidazole ligand, instead, hydrogen bonding interactions between SO₃^- and imidazole and water molecules constructed two-dimensional alternating inorganic-organic structures. Therefore, the Cu²⁺ and Co²⁺ show no tendency to coordinate to sulfonate anions in the presence of imidazole ligand in aqueous solution. p-Toluenesulfonate in complex 6 didn’t coordinate to Zn²⁺ in the presence of o-phenylenediamine. All of the SO₃^- O-atoms and the amino H-atoms, water molecules are involved in hydrogen bonds with each other, resulting extended stable structures.（3） A novel one-dimensional zinc（Ⅱ） coordination polymer [Zn（acac）₂（4,4’-bipy）]_n （7） has been synthesized and cultured using the solvothermal method in methanol medium. It’s structure was characterized by element analysis, IR, ¹H NMR and TGA. The crystal structure was determined by X-ray single-crystal diffraction. In the crystal, a plannar structure unit Cu（acac）₂ are linked with 4,4’-bipyridinyl, forming a one-dimension chain. The theoretical investigation of the complex 7 as a structure unit was carried out at HF/LanL2dz level with Gaussian 03W program, and the atomic charges distribution, composition of some frontier molecular orbitals provided a good testimony for the coordination condition in the crystal structure.（4） Three new zinc complexes [（tren）Zn（HCOO）Zn（tren）]（BF₄）₃（8）, [（tren）ZnCl]BF₄（9） and [Zn（1,2-pn）3]（ClO₄）₂（10） were obtained by the reactions of zinc salts with polyamine tris （2-aminoethyl）amine, propane-1,2-diamine respectively. X-ray diffraction analysis reveals that in complex 8 and 9, Zn（Ⅱ） ion is coordinated in a distorted trigonal bipyramids coordination geometry, while in complex 10 Zn（Ⅱ） ion adopts octahedral coordination geometry. There is moderate intermolecular hydrogen bonds between the amino hydrogens and BF₄^- fluorins in complex 8, forming 3-D layer structure. Compounds 8-10 were also characterized by element analysis, IR and H NMR.（5） Three new complexes [Ni(C₇H₁₉N₃O)₂]（ClO₄）₂（11）, [Cd(C₇H₁₉N₃O)₂]（ClO₄）₂（12） and {[Cu₂(C₇H₁₉N₃O)₂(C₁₀H₈N₂)]（ClO₄）₄·H₂0}（13） have been prepared by reaction of ligand l-[bis（aminoethyl）amino]-2-propanol （L） and 4,4’-bipyridyl with Ni（Ⅱ）, Cd（Ⅱ） and Cu（Ⅱ） ions. The products were characterized by element analysis, IR, H NMR , TGA and X-ray single-crystal diffraction analysis. In compound 11, the nickel center coordinates to two tridentate nitrogen atoms of two L ligands, leaving the other binding site hydroxypropyl pendant. Ni（Ⅱ） ion with two L ligands forms six-coordinated complex . The geometry around Ni（Ⅱ） is octahedral. The L in compound 12 is coordinated to Cd（Ⅱ） ions as tetradentate mode, so that the Cd center is eight-coordinated. This is not a familiar coordination number for the Cd（Ⅱ） ion. Eight coordination atoms form a distorted square antiprism with a Cd（Ⅱ） ion center. Compound 13 is a binuclear mixed-ligand copper（Ⅱ） complex with 4,4’-bipyridyl as bridging ligand. Each of Cu（Ⅱ） ions is bonded to three nitrogen atoms and one oxygen atom from L and one nitrogen atom from 4,4’-bipy, forming a CUN₄O five-coordinated tetragonal pyramid stereochemistry. The Cu…Cu distance in [Cu₂ (C₇H₁₉N₃O)₂(C₁₀H₈N₂)]⁴⁺ is 1.1122 nm. Thermogravimetric analysis （TGA） was performed to investigate the thermal stability of compounds 11-13. The thermal behaviour of 11 and 13 is very similar and generally shows a single-step explosive thermal decomposition at 298℃and 260℃. The results provide the valuable information for further investigations for these compounds as a potential energetic materials.更多还原