【作者】 刘丁；

【导师】 王恩波； 鹿颖；

【作者基本信息】 东北师范大学 ， 无机化学， 2014， 博士

【摘要】 多金属氧酸盐是一类具有优异物理和化学性质的无机材料，具有多样的结构和优异的分子特性，如高的负电性、氧化还原活性、可调的酸碱性和纳米尺寸结构等，使其在磁性、催化、药物等领域等具有广泛的应用前景。以具有特定功能的多金属氧酸盐作为建筑单元设计合成新型具有功能特性的多酸晶态固体材料成为多酸化学研究的主要方向之一。本文从分子设计的思想出发，采用{MnV13}体系、手性Dawson型和经典Anderson型多金属氧酸盐簇为基本建筑块，利用分子自组装、自识别以及表面修饰、剪裁等方法，在常规水溶液中合成了21种新型的基于多金属氧酸盐的晶态固体材料化合物，探讨了合成反应规律与结构和功能之间的关系。通过元素分析、红外光谱、紫外-可见光谱和单晶X-射线衍射等方法对晶体结构进行表征和分析。对化合物的热稳定性、圆二色谱性质、吸附性能、催化性质、磁学性质和电化学性质进行了初步探索。1.利用[MnV13O38]7-多阴离子通过稀土离子Ln3+(La3+和Ce3+)连接形成3个新颖的三维纯无机晶态孔材料，不仅保持着无机孔材料的稳定性，而且具有金属-有机框架材料的功能特性。可以作为非均相催化剂催化氧化噻吩类硫化物，是一种制备简单、容易回收、可重复利用、具有高活性的催化剂。并且对这类晶态孔材料的气体吸附性能进行了研究。H[La(H2O)4]2[MnV13O38]·9NMP·17H2O (1)H[Ce(H2O)4]2[MnV13O38]·9NMP·17H2O (2)H[La(H2O)4]2[MnV13O38]·8NMP·9H2O (3)2.采用常规水溶液合成方法，以稀土离子La3+，Ce3+和Nd3+作为阳离子，烟酸配体作为保护剂和结构导向剂，得到由三个[MnV13O38]7-单体通过六核稀土簇连接形成纳米尺寸的三聚体，并通过烟酸分子的氢键相互作用形成三维超分子结构。三聚体表现出很好的电催化还原亚硝酸盐的性质，磁性研究表明化合物5中存在反铁磁相互作用。这项研究提供了一种制备纳米尺寸的多酸晶态固体材料的模型反应，在电子、光学和磁性等领域都有着潜在的功能特性。H[{KLa2MnV13O38}3(SO4)2]·3(C6H6NO2)·57H2O (4)H[{KCe2MnV13O38}3(SO4)2]·3(C6H6NO2)·47H2O (5)H[{KNd2MnV13O38}3(SO4)2]·3(C6H6NO2)·45H2O (6)3.采用常规水溶液方法，以[MnV13O38]7-为前驱体，与稀土离子和DMF、异烟酸有机配体反应，得到了6个基于{MnV13}的有机-无机杂化晶态固体材料。化合物7-8中多酸建筑块被稀土-DMF配合物单元连接形成一维链，化合物9中的一维链进一步被K+连接形成三维结构。化合物10-11的结构相似，是由{Ln2(C6H5NO2)3(H2O)6}连接[MnV13O38]7-多阴离子形成一维扩展结构。有机配体在反应过程中起到保护剂的作用。进一步分析发现稀土离子的镧系收缩效应对化合物的结构有着重要的影响。化合物具有优异的电催化亚硝酸盐的活性，磁性研究表明金属中心存在反铁磁相互作用。H[{La2(DMF)5(H2O)4}{MnV13O38}]·DMF·5H2O (7)H[{Ce2(DMF)2(H2O)7}{MnV13O38}]·0.5DMF·5.5H2O (8)H2[{K(H2O)2}2{Nd(DMF)(H2O)3}{MnV13O38}]·5H2O (9)H[{La2(C6H5NO2)3(H2O)6}{[MnV13O38}]·C6H5NO2·10H2O (10)H[{Ce2(C6H5NO2)3(H2O)6}{MnV13O38}]·C6H5NO2·10H2O (11)H2.5[{Pr(C6H5NO2)(H2O)3.5}{Pr0.5(H2O)2}{MnV13O38}]·0.5C6H5NO2·10H2O (12)4.采用常规水溶液方法，以质子化的碱性氨基酸L,D-组氨酸为手性拆分试剂实现了对Dawson型手性多金属氧酸盐[P2Mo18O62]6-的化学拆分，得到了两对组氨酸修饰[P2Mo18O62]6-的对映异构体。通过对结构的比较，进一步研究了不同比例氨基酸对[P2Mo18O62]6-多阴离子手性传递的影响。这一研究不仅解决了多酸化学中近百年来关于[P2Mo18O62]6-多阴离子的拆分问题，并为其在不对称催化、手性分离及生物医药等领域的应用提供了前提和可能性。同时发展了利用手性的碱性氨基酸对外消旋的手性多酸进行拆分新途径。H3(L-HC6H9N3O2)3[P2Mo18O62]·10H2O (13)H3(D-HC6H9N3O2)3[P2Mo18O62]·10H2O (14)H4(L-HC6H9N3O2)2[P2Mo18O62]·21H2O (15)H4(D-HC6H9N3O2)2[P2Mo18O62]·21H2O (16)5.化合物17是以Anderson型[Al(OH)6O18]3-多阴离子为建筑块，通过铜-甘氨酸配合物单元和钾离子的连接形成三维开放结构。化合物18-21中[Al(OH)6O18]3-和稀土离子连接形成一维链，通过脯氨酸分子的氢键相互作用形成三维超分子结构。以化合物18为例研究这类多酸晶态固体材料在紫外光下降解罗丹明B的光催化效果。[(Gly)2Cu]K3[Al(OH)6Mo6O18]·9H2O (17)(C5H9NO2)2[La(H2O)7AlMo6H6O24]·11H2O (18)(C5H9NO2)2[Ce(H2O)7AlMo6H6O24]·11H2O (19)(C5H9NO2)2[Pr(H2O)7AlMo6H6O24]·10H2O (20)(C5H9NO2)2[Gd(H2O)7AlMo6H6O24]·10H2O (21)更多还原

【Abstract】 Polyoxometalate represent a vast class of inorganic materials with excellent physical andchemical properties, such as high negative charge, redox properties, adjustable pH andnano-sized structures, which attracted considerable promise for potential applications inmagnetic, catalysis and medicine. The design and synthesis new functional crystalline solidmaterial based on polyoxometalates using specific POM building blocks have become one ofthe main directions in POM chemistry. In this paper, we have obtained a series crystallinesolid material by using {MnV13} system, chiral Dawson-type and Anderson-typepolyoxometalates based on the point of molecular design, self-assembly, self recognition andsurface modification. The syntheses, structures and properties of these compounds wereinvestigated. With a conventional synthesis procedure, twenty-one POMs have beensynthesized, and characterized by element analysis, IR, UV-Vis and single-crystal X-rayanalysis. And the thermal stabilities, circular dichroism, adsorption, catalytic property,magnetic and electrochemical properties of the compounds have been partially investigated.1. Three3D purely inorganic porous crystalline material have been synthesized based on[MnV13O38]7-polyoxometalates and rare earth ion Ln3+(La3+and Ce3+), which possess thefeature of the stability in inorganic porous material and the versatility in MOFs. The POMinorganic porous material was employed as heterogeneous catalyst for the oxidation ofthiophenic sulfur. The result indicated that compound2is an simple preparation, easy recycle,reusable and high activity catalyst. Meanwhile, the adsorption properties of the crystallineporous material was investigated.H[La(H2O)4]2[MnV13O38]·9NMP·17H2O (1)H[Ce(H2O)4]2[MnV13O38]·9NMP·17H2O (2)H[La(H2O)4]2[MnV13O38]·8NMP·9H2O (3)2. Three trimeric polyoxovanadate based on [MnV13O38]7-polyoxoanion withlanthanide cations Ln3+(Ln=La, Ce and Nd) and nicotinic acid have been synthesized.Compound4-6representing the first example of polyoxovanadate-based trimericaggregate with rare earth ions. The electrochemical and electrocatalytic properties of thecompounds have been investigated. Magnetic studies indicate that antiferromagneticinteractions exist in the compound5. This study provides a model reaction for preparingnano-sized crystalline solid materials based on POM, which have a potential functionalcharacteristics in electronic, optical and magnetic fields.H[{KLa2MnV13O38}3(SO4)2]·3(C6H6NO2)·57H2O (4) H[{KCe2MnV13O38}3(SO4)2]·3(C6H6NO2)·47H2O (5)H[{KNd2MnV13O38}3(SO4)2]·3(C6H6NO2)·45H2O (6)3. A series of {MnV13}-based inorganic-organic hybird compounds have beenconstructed by using [MnV13O38]7-, rare earth ions, DMF and isonicotinic acid underconventional aqueous solution method. The {MnV13} building blocks in compounds7-8are connected by rare earth-DMF complex to form a one-dimensional chain. Incompounds10-11,[MnV13O38]7-polyoxoanions were linked by {Ln2(C6H5NO2)3(H2O)6}to obtained a one-dimensional structure. The organic ligands play the role of theprotective and templating agents in the reaction. Furthermore, lanthanide contractionphenomenon of rare earth ions lead to a significant impact on the structure of thecompounds. The electrochemical and electrocatalytic properties of the compounds havebeen investigated. Magnetic studies indicate that antiferromagnetic interactions exist inthe compounds.H[{La2(DMF)5(H2O)4}{MnV13O38}]·DMF·5H2O (7)H[{Ce2(DMF)2(H2O)7}{MnV13O38}]·0.5DMF·5.5H2O (8)H2[{K(H2O)2}2{Nd(DMF)(H2O)3}{MnV13O38}]·5H2O (9)H[{La2(C6H5NO2)3(H2O)6}{[MnV13O38}]·C6H5NO2·10H2O (10)H[{Ce2(C6H5NO2)3(H2O)6}{MnV13O38}]·C6H5NO2·10H2O (11)H2.5[{Pr(C6H5NO2)(H2O)3.5}{Pr0.5(H2O)2}{MnV13O38}]·0.5C6H5NO2·10H2O (12)4. The chiral Dawson-type polyoxoanions [P2Mo18O62]6-racemic have beenseparated in aqueous solution with L,D-histidine, respectively. Two pairs ofenantiomerically compounds have been synthesized. We have also study the effects ofdifferent amino acids proportion for chiral transfers. Provides the premise applications ofthe chiral Dawson-type [P2Mo18O62]6-in the field of asymmetric catalysis, chiralseparation and biomedical.H3(L-HC6H9N3O2)3[P2Mo18O62]·10H2O (13)H3(D-HC6H9N3O2)3[P2Mo18O62]·10H2O (14)H4(L-HC6H9N3O2)2[P2Mo18O62]·21H2O (15)H4(D-HC6H9N3O2)2[P2Mo18O62]·21H2O (16)5. A series of high-dimensional hybird POM crystalline solid material have beensynthesized by Anderson-type [Al(OH)6O18]3-as building blocks and aminoacid-transition metal or rare earth coordination complexes as functional unit. Compounds18-21are built up of polyoxoanions [Al(OH)6O18]3-linked by rare-earth cations to form aone-dimensional chain, then adjacent chains are further connected by hydrogen bonds ofproline and free water molecules to3D supramolecular structure. The photocatalystproperty of compound18indicating an excellent photocatalyst of RhB dye underUV-irradiation. [(Gly)2Cu]K3[Al(OH)6Mo6O18]·9H2O (17)(C5H9NO2)2[La(H2O)7AlMo6H6O24]·11H2O (18)(C5H9NO2)2[Ce(H2O)7AlMo6H6O24]·11H2O (19)(C5H9NO2)2[Pr(H2O)7AlMo6H6O24]·10H2O (20)(C5H9NO2)2[Gd(H2O)7AlMo6H6O24]·10H2O (21)更多还原