【作者】 高洁；

【导师】 卢会杰； 樊耀亭；

【作者基本信息】 郑州大学 ， 有机化学， 2003， 硕士

【摘要】 本论文设计合成了两个系列共8种新型类二联吡啶和类三联吡啶化合物，并用元素分析、红外、核磁、差热等手段对结构进行了鉴定。还得到了12种化合物与金属离子的配位化合物，研究了它们的结构和性能。 一、在碳酸钠存在下，对二氯甲基苯和苯并咪唑反应，得到对二（1-苯并咪唑甲基）苯（L₁）；对二氯甲基苯和2，4-戊二酮反应，得到对二[3-（2，4-戊二酮）甲基]苯（L₂）；对二[3-（2，4-戊二酮）甲基]苯（L₂）与盐酸羟胺或水合肼反应则分别得到对二[4-（3，5-二甲基异恶唑）甲基]苯（L₃）和对二[4-（3，5-二甲基吡唑）甲基]苯（L₄）。二乙酰琥珀酸二乙酯与水合肼反应得到[（3，3′-二甲基）-（5，5′-二羟基）]-4，4′-二吡唑（L₅）。 研究了这些配体与金属盐的配位性能。在常温常压条件下，得到了对二（1-苯并咪唑甲基）苯（L₁）与Cu（NO₃）₂、MnCl₂和CdCl₂等过渡金属盐的配合物。单晶衍射分析表明，配合物[Cu（Ⅱ）（NO₃）₂（L₁）]_n（1）具有扭曲的四面体结构，每个铜原子与两个L₁分子中的各一个N原子和两个NO₃^-根上的O原子配位。Cu（NO₃）₂和双齿的L₁连接成“之”字形的链。配合物[Mn（Ⅱ）Cl₂（L₁）₂]_m（2）和[Cd（Ⅱ）Cl₂（L₁）₂]_m（3）则具有二维菱形栅结构，金属离子处在扭曲的八面体结构中。 当对二（1-苯并咪唑甲基）苯（L₁）与氯化锌（Ⅱ）在含有少量盐酸的甲醇溶液中反应时生成超分子化合物[H₂（L₁）ZnCl₄]·H₂O。晶体结构中，Zn²⁺离子与四个Cl^-离子配位并通过H-键与质子化的L₁和H₂O相连形成一个三维的超分子化合物： 二、在含二乙胺的三乙胺存在下，以三氯均三嗦与3，5一二甲基毗哇作用，得到了化合物2，4一双（3，5一二甲基毗哇卜6一二乙胺基一1，3，5一均三嗦（L6）;若在碳酸钠存在下，三氯均三嗦与3，5一二甲基毗哇作用则得到2，4，6一三（3，5一二甲基毗哇）均三嗦（Ls）;同样的，在碳酸钠存在下，三氯均三啧与2，4--戊二酮作用则得到2，4，6一三[3一（2，4-戊二酮）]均三嗦（L7）。常温下得到了L6与Y，，‘、Lal，，、ee，，，、Prl，，、Nd“‘和EuI，，等稀土金属离子形成的配合物。斓系的五个配合物属同形同构体: 配合物中，未配位的配体和配位的水通过氢键相连。配位的配体和未配位的配体之间通过二一二相互作用堆积起来。忆的配合物[Y L6困03）3』的结构不同于斓系的几个配合物，前者为九配位而后者为十配位。同时还得到了CoL6C12和MnL6C12两个配合物，对它们的结构进行了分析。 三、用固体粉末在室温下得到斓系配合物的发射光谱，结果表明只有Eum的配合物有较强的金属荧光，其它的化合物没有这种现象。研究了铺的配合物的荧光光谱，发现由于配位作用，铺的荧光性能得到了加强。这是由于类三联毗睫这类化合物发色基团与悯系金属离子配位能够吸收能量并且有效的转移给阳离子或者防止了其与溶剂（特别是HZo）的作用，阻抑了溶剂对斓系离子的荧光碎灭，极大地提高了发光效率。 本文所得到的化合物和配合物均未见文献报道。更多还原

【Abstract】 In this thesis, eight new bipyridine-like or terpyridine-like compounds in two series were synthesized and charactered by Elemental analyses, IR spectra, ’HNMR, Thermal analyses etc. With these compounds, 12 coordination polymers were obtained and their crystal structures and properties were studied.1. In the presence of potassium carbonate, a, a’-dichlor-p-xylene reacted with Benzimidazole to give 1,4-bis(l-benzimidazolylmethyl)benzene(Li) in high yield. When a,a’-dichlor-p-xylene reacted with 2,4-pentanedione, 1,4-bis[2,5-dioxy- 3-pentylmethyl] benzene (L2) was obtained. The LI reacted further with hydroxylamine or hydrazine to give l,4-bis[4-(3,5-dimethyl-l-isoxazolyl)methyl] benzene(L3) and 1,4-bis[4-(3,5-dimethyl-1 -pyrazolyl)methyl] benzene(L4), respectively. Diethyl-2,5-diacetylsuccinate reacted with hydrazine to give (3,3-dimethyl)-(5,5-di)-4,4-dipyrazole(L5).The coordination properties of the above compounds were studied. Three novel coordination polymers of LI with metal ions, [Cu(II)(NO3)2(Li)]n (1), [Mn(II)Cl2(Li)2]m (2) and [Cd(II)Cl2(Li)2]m (3) were obtained. X-ray single crystal diffraction analysis showes that polymer 1 exhibits a distorted tetrahedron, in its structure the mental atom is coordinated by two nitrogen atoms from two LI and two oxygen atoms from two NOs" groups. Each Cu(II)(NO3)2 unit is bridged by LI to form a zigzag chain structure; Polymer 2 and 3 are two-dimensional network. The coordination environment of Mn(II) and Cd(II) are a distorted octahedron.In the presence of hydrochloric acid, 1,4-bis(l-benzimidazolylmethyl) -benzene(Li) reacted with zinc chloride to give a new supramolecular complex of [H2(Li)ZnCLi]-H2O. The crystal structure showes that the zinc(II) atom is coordinated by four chloride ions and connected with protonated LI and H2O through H-bonding, thus forming a 3-d2. In the presence of triethylamine containing about 11% diethylamine , 2,4-Bis(3,5-dimethyl-1-pyrazolyl)-6-diethylamino-1,3,5-triazine(L6) was obtained by the reacted of 2,4,6-trichloro-l,3,5-triazine with 3,5-dimethylpyrazole. But in the presence of potassium carbonate, 2,4,6-trichloro-l,3,5-triazine reacted with 3,5-dimethylpyrazole to give 2,4,6-tris(3,5-dimethyl-l-pyrazolyl)-l,3,5-triazine(L8). When 2,4,6-trichloro-l,3,5 -triazine reacted with 2,4-pentanedione in the presence of potassium carbonate, 2,4,6-tri(2,5-dioxy-3-pentylmernyl)-1,3,5-triazine(L7) was obtained. The complexes of L6 with Y, La, Ce, Pr, Nd and Eu were obtained. The structures of these complexes, [YL6(NO3)3] (1) and [LnL6(NO3)3(H2O)]L6 (Ln=La, 2; Ce, 3; Pr, 4; Nd, 5; Eu, 6), have been determined by x-ray crystal structural analysis.The structures of the five lanthanoid complexes are isomorphous and isostructural, which are different from the crystal structure of the Yttrium complex [YL6(NO3)3]. Thelatter shows a nine coordinate metal center but the crystal structure of the lanthanoid complexes [LnL6(NO3)3(H2O)]L6 are ten-coordinate metal center. The TC-TC stacking and hydrogen bonding between the coordinated and uncoordinated Le molecules sensitized the Ln luminescence. The thermal behavior of the ligand and its complexes are also discussed. The complexes of Co(1) and Mn(2) with 2,4-bis(3,5-dimethylpyrazol-1-yl)-6-diethylin-1,3,5-triazine were synthesized and and studied their structure.3. The luminescence spectra of the powdered solid complexes were obtained for at room temperature. The results show that only Eu complex have the properties of luminescence. Study of the luminescence spectra shows that the special molecular chelating structure of terpyridine and the terpyridine-like compounds can enhance the luminescence of lanthanide substantially.All the compounds and complexes were not reported.更多还原