基于芳香多羧酸和双吡啶噁二唑类混合配体的配位聚合物的合成、表征及性质研究

【作者】 楼佳颖；

【导师】 翁林红；

【作者基本信息】 复旦大学 ， 物理化学， 2010， 硕士

【摘要】 本论文致力于双吡啶类桥连配体和多羧酸类配体的混合配位聚合物材料的研究。通过建立不同的反应体系,成功合成得到了十三个新型的配位聚合物,通过X-射线单晶衍射结构分析和元素分析(EA),对部分配位聚合物还利用X-射线粉末(XRD)表征其相对纯度,并进行了红外(IR)和热重分析(TGA)等相关表征以及固体荧光性质的研究。论文主要分为三个部分：一、以金属镍离子或锌离子为金属中心,基于2,5-二(3-吡啶)-1,3,4噁二唑(3-bpo)与芳香多羧酸类配体(H3btc,p-H2bdc,m-H2bdc)的混合配体体系,分别得到了6个无限一维链结构的配位聚合物：[Ni(3-bpo)(Hbtc)(H2O)2]n·(H2O)n(JL-1), [Ni(3-bpo)(m-bdc)(C2H5OH)2]n (JL-2), [Ni(3-bpo)(m-bdc)(H2O)]n·(H2O)n (JL-3), [Ni(3-bpo)2(p-bdc)(H2O)2]n·2(H2O)n (JL-4), [Zn(3-bpo)(Hbtc)(H2O)]n·(H2O)n (JL-5), [Zn(3-bpo)2(p-bdc)(CH3OH)2]n·2(CH3OH)n(JL-6)。研究了不同的金属中心,溶剂,等因素对配位聚合物合成的影响,并对它们进行了结构解析和性质表征。其中,JL-1,JL-4,JL-5和JL-6还通过氢键和π…π共轭等弱相互作用形成了三维超分子网络结构。二、以金属锌离子,镉离子或镍离子为金属中心,基于2,5-二(3-吡啶)-1,3,4嗯二唑(3-bpo)或2,5-二(4-吡啶)-1,3,4嗯二唑(4-bpo)和芳香多羧酸(o-H3btc, p-H2bdc, m-H2bdc)组成的混合配体体系,得到了四个具有较高维度的配位聚合物：[Zn2(4-bpo)(o-bdc)2]n (JL-7), [Ni(3-bpo)(p-bdc)]n·(H2O)4n (JL-8) [Cd(4-bpo)(m-bdc) (H20)]n (JL-9), [Cd2(m-bdc)2(3-bphH2)(H2O)2]n (JL-10), X-射线单晶衍射分析表明,JL-7是一个具有(46·64)拓扑结构的致密的三维骨架结构,JL-8和JL-9的结构为(4,4)连接的二维格子网络,而JL-10是一个具有(4·64·8)(42·63·8)的新型拓扑结构的二维网络,并由氢键形成了三维的超分子网络。我们还发现,JL-10是3-bpo通过酸性配体催化,高温下原位开环反应成3-bphH2得到的配位聚合物。三、以金属镍离子或钴离子为金属中心,2,5-二(3-吡啶)-1,3,4嗯二唑(3-bpo)和羧酸类配体作为混合配体体系,得到了3个零维的配合物,分别为[Ni2(3-bpo)2(Ac)4(H2O)4]·2(H2O)(JL-11), [Ni2(3-bpo)2(m-bdc)2(CH3OH)4]·2(CH3OH) (JL-12), [Co2(3-bpo)2(m-bdc)2(H2O)4]·2(3-bpo)·4(C3H7OH) (JL-13), X-射线单晶衍射分析表明,这3个配合物都是以M204N2的八面体配位方式配位。其中JL-11是一个具有离散的双金属环结构的超分子配合物,JL-12和JL-13由于引入了间苯二甲酸与3-bpo组成混合配体体系,故形成了离散的具有双金属笼状结构的超分子配合物,分子间存在弱π…π相互作用。我们还对部分配位聚合物的热稳定性和荧光性质进行了测试,通过热重分析,发现它们都具有较高的热稳定性。通过固体荧光测试,发现它们表现出强烈的蓝色固体荧光,可以作为潜在的光致发光材料。更多还原

【Abstract】 The work of this thesis focuses on the preparation of metal organic frameworks based on mixed ligands system of dipyridyl ligands and multi-carboxylate acid ligands. We successfully obtained 13 novel coordination polymers in different reaction conditions. X-ray single-crystal diffraction, elemental analysis (EA), infrared spectroscopy (IR) and thermogravimetric analysis (TGA) were performed. The soild luminescent properties of some materials are also investigated. There are mainly three parts in this thesis:First, we prepared MOFs based on 2,5-bis (3-pyridyl)-1,3,4-oxadiazole (3-bpo) and multicarboxylic acid (H3btc,p-H2bdc,m-H2bdc). We chose Ni(II) and Zn(II) to coordinate with the mixed ligands and obtained six one-dimensional complexes: [Ni(3-bpo)(Hbtc)(H2O)2]n·(H2O)n (JL-1), [Ni(3-bpo)(m-bdc)(C2H5OH)2]n (JL-2), [Ni(3-bpo)(m-bdc) (H2O)]n-(H2O)n (JL-3), [Ni(3-bpo)2(p-bdc) (H2O)2]n·2(H2O)n (JL-4), [Zn(3-bpo)(Hbtc) (H2O)]n·(H2O)n (JL-5), [Zn(3-bpo)2(p-bdc)(CH3OH)2]n 2(CH3OH)n (JL-6), we also investigated how the metal center and solvent affect on the synthesis and structures of the compounds. Their structures have been determined by single crystal X-ray diffraction analyses. In addition, JL-1, JL-4, JL-5 and JL-6 generate 3D supramolecular networks through hydrogen bond andπ…πinteraction.Second, we obtained four higher dimension MOFs based on the 3-bpo,4-bpo and multicarboxyl acids (o-H3btc,p-H2bdc, m-H2bdc) by the hydrothermal reaction with metal salts Zn(II), Ni(II) and Cd(II):[Zn2(4-bpo) (o-bdc)2]n (JL-7), [Ni(3-bpo) (p-bdc)]n·(H2O)4n (JL-8), [Cd(4-bpo)(w-bdc)(H2O)]n (JL-9), [Cd2(m-bdc)2(3-bphH2) (H2O)2]n (JL-10). The single-crystal X-ray diffraction measurement reveals that JL-7 is a compact (46·64) 3D net while JL-8 and JL-9 shows a (4,4) 2D grid net. JL-10 shows a (4·64·8) (42·63·8) 2D net and pack to 3D supramolecular networks through hydrogen bond. The 3-bphH2 ligand of JL-10 was obviously in situ generated from the starting materials 3-bpo via a hydrolysis reaction along with the ring-open of the oxadiazole ring.Third, we designed and synthesized complexes based on the 2,5-bis(3-pyridyl)-1, 3,4-oxadiazole (3-bpo) and carboxylic acid ligand. We chose Co(II) and Ni(II) to coordinate with mixed ligands and obtained three zero-dimensional complexes:[Ni(3- bpo)(CH3COO-)2(H2O)2]·(H2O) (JL-11), Ni(3-bpo)(m-bdc)(CH3OH)2]·(CH3OH) (JL-12), [Co2(3-bpo)2(m-bdc)2(H2O)4]-2(3-bpo)-4(C3H7OH)(JL-13). The single-crystal X-ray diffraction measurement reveals that the metal center lies in the center of a little distorted octahedral environment. JL-11 is a discrete bimetal circle while JL-12 and JL-13 exhibit bimetal cages due to the introduction of m-H2bdc. The complexes were packed through weakπ…πreactionIn addition, The thermal stability and fluorescent properties of some materials have been investigated, they present high thermal stability and show great blue solid luminescent properties, which can be utilized as a kind of potential photo-luminescent materials.更多还原