新型钒多酸基金属有机多面体的结构、自组装合成和性能研究

发布时间：2018-07-29 05:50

【摘要】：金属有机多面体(MOPs)是继分子筛和金属有机框架(MOFs)之后,又一类发展迅速的多孔材料。MOPs不是无限的三维网络结构,而是孤立的分子实体;它们构建于边共享的分子多边形或通过分子顶点之间的相互连接而成。基于金属与有机配体自组装形成的分子多面体,其具有纳米尺度的笼形结构以及内、外表面积。同时,MOPs具有灵活的几何拓扑,尺寸,表面积和孔性。它们可以作为主体分子,在许多领域具有重要的应用,包括催化,吸附,生物物理学,还可以作为前驱体去构建MOFs材料。多金属钒酸盐(POVs),作为多酸的一个独特的分支,一直吸引人们的研究兴趣,因为钒多酸不仅具有结构多样性和卓越的特性,而且它们在分子磁学,催化,氧化还原,医学,生物活性材料等方面有潜在应用。本论文选择简单的金属钒源和不同的羧酸配体设计合成了13个钒多酸基金属有机多面体。在特定的溶剂热条件下,我们得到了新颖的具有不同配位模式的钒多酸基建筑块,这对于MOPs的形成起到了关键作用。由于得到化合物的骨架中存在还原态的钒,我们对大部分化合物的磁性进行了探索。1.我们的策略是利用钒多酸和线型二羧酸配体构建钒多酸基有机无机杂化材料。最终得到了三种同构的基于金属{V_5O_9Cl}单元的金属有机八面体配位笼。通过单晶X射线衍射,粉末射线衍射,红外,热重以及N2吸附等手段对这些化合物进行了表征(NH_2Me_2)12[(V_5O_9Cl)6(BDC)12]·(DMF)17(1)(NH_2Me_2)12[(V_5O_9Cl)6(BDC-NH_2)12]·(DMF)14(2)(NH_2Me_2)12[(V_5O_9Cl)6(BDC-Br)12]·(DMF)8(3)BDC=1,4-对苯二甲酸BDC-NH_2=2-氨基-对苯二甲酸BDC-Br=2-溴-对苯二甲酸2.我们采用角形配体或尺寸加成的双齿羧酸配体与钒氧簇自组装,成功的获得了三种新颖的钒多酸基金属有机多面体;其结构中都含有{V_5O_9Cl}建筑单元。有趣地是,由于配体性质的不同,它们的结构呈现差异性,包括截角三棱柱、截角四棱锥和截角八面体结构。此外,磁性研究表明他们具有相似的铁磁性行为。(NH_2Me_2)6[(V_5O_9Cl)3(TDA)6]·(DMF)1.5(CH3OH)0.5(4)(NH_2Me_2)8[(V_5O_9Cl)4(m-BDC)8]·(DMF)3(CH3OH)0.5(5)(NH_2Me_2)12[(V_5O_9Cl)6(NDC)12]·(DMF)8(CH3CH_2OH)0.5(6)TDA=噻吩-2,5-二羧酸m-H_2BDC=间苯二甲酸2,6-H_2NDC=2,6-萘二甲酸3.我们对五种新颖的烷氧基修饰的钒多酸基金属有机多面体的溶剂热合成、结构进行了报道。同时,对其中三种化合物的磁性进行了研究;结果表明他们都具有反铁磁性相互作用。据我们所知,此工作将烷氧基修饰的钒多酸引入到金属有机材料当中,这是比较罕见的。{V6S}建筑单元的发现不仅为有限的钒多酸家族增加了一个典型的实例,而且它作为一个三连接的无机配体,适合与有机配体自组装构建截角四面体结构或分子胶囊。(NH_2Et_2)8{[V6O6(OCH3)9(SO4)]4(BDC)6}(DEF)2(7)(NH_2Et_2)8{[V6O6(OCH3)9(SO4)]4(BDC-NH_2)6}(DEF)1.5(8)(NH_2Et_2)8{[V6O6(OCH3)9(SO4)]4(BDC-Br)6}(DEF)1(9)(NH_2Et_2)8{[V6O6(OCH3)9(SO4)]4(BTC)4}(DEF)0.5(10)(NH_2Et_2)8{[V6O6(OCH3)9(SO4)]4(BTB)4}(DEF)1.5(11)BTC=1,3,5-均苯三甲酸;BTB=1,3,5-三(4-羧基苯基)苯4.基于我们之前的工作,在相似的溶剂热条件下,我们使用三氯化钒替换硫酸氧钒,得到了两例含有新型{V_7}同多酸簇的钒基金属有机多面体。他们呈现精美的截角四面体笼形结构。此外,这种{V_7}多酸基建筑单元是首次被发现,与文献报道的钒基MOPs相比,其具有最高核数的钒氧簇。磁性研究表明他们具有相似的反铁磁行为。(NH_2Et_2)4{[V6O6(OCH3)9(VO3)(H_2O)]4(BDC)6}(DEF)0.5(12)(NH_2Et_2)4{[V6O6(OCH3)9(VO3)(H_2O)]4(BDC-NH_2)6}(DEF)0.5(CH3OH)0.5(13)
[Abstract]:Metal organic polyhedron (MOPs) is followed by molecular sieves and metal organic frameworks (MOFs). Another fast developing porous material,.MOPs, is not an infinite three-dimensional network structure, but an isolated molecular entity; they are constructed of polygons shared by the side or interconnected through the top of the molecule. Based on metal and organic ligands The molecular polyhedron formed by self assembly has a nanoscale cage structure as well as inside, surface area. At the same time, MOPs has a flexible geometric topology, size, surface area and porosity. They can be used as the main molecules in many fields, including catalysis, adsorption, biophysics, and can be used as precursors to build MOFs. Material. Polymetallic vanadate (POVs), as a unique branch of polyacid, has attracted people's interest in research, because vanadate not only has structural diversity and excellent properties, but also has potential applications in molecular magnetism, catalysis, oxidation-reduction, medicine, bioactive material and so on. This paper chooses a simple metal vanadium source. 13 vanadium polyacid based polyhedron are designed and synthesized with different carboxylic ligands. Under specific solvent thermal conditions, we have obtained a novel vanadium polyacid base with different coordination modes, which plays a key role in the formation of MOPs. The magnetic properties of the compounds are explored.1. our strategy is to use vanadate and linear two carboxylic acid ligands for the construction of vanadium polyacid organic-inorganic hybrid materials. Finally, three isomorphic metal organic eight surface coordination cages based on metal {V_5O_9Cl} elements are obtained. By single crystal X ray diffraction, powder ray diffraction, infrared, thermo gravimetric and N2 absorption. NH_2Me_2 12[(V_5O_9Cl) 6 (BDC) 12]. (DMF) 17 (DMF) 17 (NH_2Me_2) 12[(NH_2Me_2) 12[(V_5O_9Cl) 6 (BDC-NH_2) 12] (BDC-NH_2) 14 (2) 6 (3) 8 (3) used angular ligands for benzoic acid terephthalic terephthalic terephthalic acid terephthalic terephthalic terephthalic acid (3). Three kinds of novel vanadium polyacid base metal polyhedron are successfully obtained by self assembly of the size addition dicarboxylic carboxylic ligands and vanadium oxygen clusters. The structure contains {V_5O_9Cl} building units. Interestingly, their structure is different because of the different ligand properties, including the truncated three prism, the truncated four pyramid and the truncated eight face structure. In addition, magnetic properties show that they have similar ferromagnetic behavior. (NH_2Me_2) 6[(V_5O_9Cl) 3 (TDA) 6]. (DMF) 1.5 (CH3OH) 0.5 (CH3OH) 0.5 (NH_2Me_2) 8[(V_5O_9Cl) 4 (m-BDC) 8]. 3 (8) 8 (6) 8 (6), 8 (6), 8 (6) Acid 3., we reported the structure of the solvothermal synthesis of five novel alkoxy modified vanadium polyhedron polyhedron. Meanwhile, the magnetic properties of three of these compounds were studied. The results show that they all have antiferromagnetic interaction. In organic materials, the discovery of this rare.{V6S} building unit is not only a typical example of a limited vanadate family, but also as a three connected inorganic ligand, suitable for the construction of a truncated tetrahedral structure or molecular capsule with organic ligand. (NH_2Et_2) 8{[V6O6 (OCH3) 9 (SO4)]4 (BDC) 6} (DEF) 2 (7) (N) (N) H_2Et_2) 8{[V6O6 (OCH3) 9 (SO4)]4 (BDC-NH_2) 6} (DEF) 1.5 (NH_2Et_2) 8{[V6O6 (OCH3) 9 (SO4) 1 (9) 0.5 (10) 9 (11) Under the solvothermal condition, we use three vanadium chloride to replace vanadium sulfate, and two cases of vanadium based metal organic polyhedron containing a new {V_7} polyacid cluster. They present a fine truncated tetrahedral cage structure. In addition, this {V_7} polyacid base building unit is first discovered, and is the highest compared with the reported vanadium base MOPs. Nuclear number of vanadium oxygen clusters. Magnetic studies show that they have similar antiferromagnetic behavior. (NH_2Et_2) 4{[V6O6 (OCH3) 9 (VO3) (H_2O)]4 (BDC) 6} (DEF) 0.5 (12) (NH_2Et_2) 4{[V6O6 (OCH3) 9 (OCH3) 0.5 (13) 0.5 (13)
【学位授予单位】：东北师范大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O641.4

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