【作者】 昆道列提·艾力木阿吉；

【导师】 彭军；

【作者基本信息】 东北师范大学 ， 无机化学， 2013， 博士

【摘要】 本论文选用杂多钨、钼酸盐为无机建筑块，选择不同的有机含氮多齿配体和金属离子，构筑了一系列新颖的有机无机杂化化合物。探讨了各种不同反应条件对产物晶体结构的影响规律，并探索合成的新物质的结构与其性能间的关系。利用水热条件下合成的技术，通过调节反应的各种条件和反应的不同原料等，合成了12种基于多金属钨、钼酸盐的有机无机杂化化合物及混合性铌配合物。通过元素分析、红外光谱、热重分析、X-射线粉末衍射，光电子能谱和X-射线单晶衍射等手段对得到的这些晶体的结构进行了表征，并且对这些化合物的电化学、荧光性质进行了初步研究。1.以Keggin型钨酸盐作为无机建筑块，选择不同有机胺多齿配体和配位模式丰富的d¹⁰金属Zn^Ⅱ和Cd^Ⅱ阳离子，在水热反应条件下合成并表征了6个新的有机无机杂化化合物：[Zn（phen）₂]₂(PWVIV11WO₄₀)（1）K[Zn（phen）₂（H₂O）]₂（OH）(SiW₁₂O₄₀)·H₂O（2）[Zn （bipy）₂（H₂O）]₂(SiW₁₂O₄₀)·H₂O （3）[Zn₂（H₂biim）₅](SiW₁₂O₄₀)·2H₂O （4）[Cd （phen）₂]₂(SiW₁₂O₄₀)（5）[Cd （bipy）₂]₂(SiW₁₂O₄₀)（6）phen=1,10-phenaanthrolinebipy=2,2’-bipyridineH₂biim=2,2’-biimidazole化合物1-3的基本结构单元都是锌的配合物双支撑的Keggin型多金属钨酸盐。化合物1是一种杂多蓝化合物，其结构中的双支撑多金属钨酸盐，通过相邻的邻菲罗啉配体之间的π…π堆积作用形成三维超分子结构。化合物2中相邻的两个双支撑keggin型多酸簇通过K⁺离子的桥接形成一维无限链结构。化合物3的结构相似于化合物1。化合物4是由一个Keggin型[SiW₁₂]多阴离子和一个二核[Zn₂（H₂biim）₅]4簇构成的超分子化合物。化合物5是Cd的配合物双支撑的Keggin型杂多钨酸盐，而化合物6是Cd的配合物四支撑的Keggin型杂多钨酸盐。据我们所知，Cd的配合物双支撑的和四支撑的Keggin型杂多钨酸盐到现在为止未见文献报道。另一方面，d¹⁰金属Zn和Cd不仅具有配位模式丰富的特点,而且具有优良的发光性能。研究结果表明化合物1-6都有荧光性质。2无机建筑块，合成了两个未见文献报道的有机-无机杂化化合物,做了荧光性质的初步研究:[Cu₂（H₂biim）₂（μ2-OH）₂]₂[SiW₁₂O₄₀]（7）[Cu（H₂biim）₂（OH）][Cu（H₂biim）₂]{Cu（H₂biim）₂[BW₁₂O₄₀]}·3H₂O （8）化合物7由Cu二聚体[Cu₂（H₂biim）₂（μ2-OH）+2]₂和Keggin型多阴离[SiW412O₄₀]-构成的四支撑二维结构的化合物。在二聚体片段中，两个Cu间的距离为2.588，铜之间存在着较强的金属-金属作用，这可能是化合物7具有荧光发射的主要原因。化合物8的结构中存在晶体学上独立的三种Cu-H₂biim配合物片段,通过两种不同的π…π堆积作用形成该化合物的三维超分子结构。3.以[P₄Mo₆]型或Keggin型多金属钼酸盐作为无机建筑块，选择不同的有机胺多齿配体和金属阳离子，在水热条件下合成并表征了3个新型的有机无机杂化化合物：（H₂en）4（en）₂{Na0.5[Mo₆O₁₅（HPO₄）（H₂PO₄）3]}{Na0.5[Na2（H₂O）₅Mo₆O₁₅（PO₄）（HPO₄）（H₂PO₄）₂]}·10H₂O （9）（H.2en）12K2（H₂O）₂Na[H19K(P₄Mo₆O₃₁)₂]₂6H₂O （10）[Cu（2,2’-bipy）]6[(PMoVIV11MoO₄₀)][（Mo6O22）].H₂O （11）化合物9和10是以M[P₄Mo₆O₃₁]₂（M＝Na,K）二聚体为基本单元的化合物。化合物9的基本结构单元为Na[Mo6P4]₂二聚体，每个二聚体与相邻的四个{NaO6}八面体相连形成带有孔道的一维链。化合物10是Na和K混合金属桥的单元结构M[P₄Mo₆O₃₁]₂构成的。最值得一提的是在化合物10的二维结构中存在着两种类型的一维隧道。化合物11是[Mo8-6O22]同多阴离子和[PMoVI11MoVO₄₀]4-杂多阴离子簇通过[Cu（2,2’-bipy）]₂+配合物以交叉的形式链接延伸形成一维长链的化合物。这个化合物{Mo6}-Cu-{PMo12}长链中存在的{Mo6}簇是很罕见的结构单元。4.使用氢氟酸溶解Nb2O5的方法，在铜离子和有机含氮配体邻菲罗啉的存在下，经过水热反应成功合成了一个新型铌－铜混合配合物：[Cu₂（phen）4（NbF₄）₂（μ-O）₂（μ-F）][NbF₆]（12）化合物12中两个Cu(C₁₂H₈N₂)₂O和两个NbOF₅配合物基团通过O、F原子桥连而构筑的。这种F原子起桥连作用的情况是很少见的。该化合物具有荧光，热稳定性高，而且难溶于水。因此化合物12可能是一个潜在的固体荧光发射材料。更多还原

【Abstract】 In this thesis, a series of organic-inorganic hybrid materials with interestingarchitectures have been obtained by the assembly of polyoxotungstates orpolyoxomolybdates, different organic ligands and metal cations. We have investigatedthat the reaction conditions, could affect the structure of the products. Further, someproperties of the compounds have been investigated, and the relationships betweenstructures and property for these new compounds are studied.Herein, Twelve Polyoxotungstates or Polyoxomolybdates based organic-inorganichybrids and Niobium Mixed Complex have been synthesized byhydrothermalsynthesis methods. These compounds have been structurally characterized byelemental analyses, IR, TG, XRPD and single crystal X-ray diffractions. Further,electrochemical and photoluminescence properties have been studied.1. Ten new orgainic-inorganic hybrid compounds based on KegginPolyoxotungstates, organic ligands and d¹⁰metals Zn₂+or Cd2+cations have beensynthesized under hydrothermal conditions:[Zn（phen）₂]₂(PWVI11WVO₄₀)（1）K[Zn（phen）₂（H₂O）]₂（OH）(SiW₁₂O₄₀)·H₂O （2）[Zn （bipy）₂（H₂O）]₂(SiW₁₂O₄₀)·H₂O （3）[Zn₂（H₂biim）₅](SiW₁₂O₄₀)·2H₂O （4）[Cd （phen）₂]₂(SiW₁₂O₄₀)（5）[Cd （bipy）₂]₂(SiW₁₂O₄₀)（6）phen=1,10-phenaanthrolinebipy=2,2’-bipyridineH₂biim=2,2’-biimidazoleIn compounds1-3, the basic structural unit is the same, that is, Zn（II） complexesare linked by the bi-supporting Keggin clusters. Compound1isa heteropoly blue, which is a three-dimensional supramolecular structure formed bythe π π stacking interactions between bi-supporting polytungstates. Compound2is aone-dimensional chain formed by K⁺ions bridging two adjacentbi-supporting Keggin clusters. The structure of compound3is similar to that ofcompound1. Compound4is a supramolecular compound composed ofKeggin type [SiW₁₂] anions and dinuclear [Zn₂（H₂biim）₅]4+clusters.Compound5is a bisupporting Keggin-type polyoxotungstate linked to Cd complex, while compound6is a tetra-supporting Keggin cluster linked to Cdcomplex. As far as we know, no compounds relating toKeggin-type polyoxotungstates linked to two or four Cd complexes have beenreported in the literature. On the other hand, the d¹⁰metal, like Zn and Cd, not onlypossesses variable coordination modes, but also has excellent luminescenceproperties. The results show that compounds1-6have relativelystrong fluorescence properties.2. Two hybrid compounds based on the Keggin Polyoxotungstates,2,2’-biimidazole ligand and Copper cations have been obtained under hydrothermalconditions:[Cu₂（H₂biim）₂（μ2-OH）₂]₂[SiW₁₂O₄₀]（7）[Cu（H₂biim）₂（OH）][Cu（H₂biim）₂]{Cu（H₂biim）₂[BW₁₂O₄₀]}·3H₂O （8）Compound7is a two-dimensional layer constructed by twodimers [Cu₂（H₂biim）₂（μ2-OH）₂]₂+and Keggin-type anionic clusters [SiW₁₂O₄₀]⁴-. Inthe dimer, the distance between of two Cu（II） is2.588, suggesting thestrong metal metal effects. In addition, relatively strong fluorescence emission canbe found for compound7. In compound8, there are three kinds of crystallographicunique Cu（II） ions. The three-dimensional supramolecular structure of8is formedby two different π π interactions among three kinds of Cu-H₂biim complexes.3. The [P₄Mo₆] or keggin type polyoxomolybdates has been chosen as inorganicbuilding blocks, and three compounds have been obtained under hydrothermalcondition:（H₂en）4（en）₂{Na0.5[Mo₆O₁₅（HPO₄）（H₂PO₄）3]}{Na0.5[Na2（H₂O）₅Mo₆O₁₅（PO₄）（HPO₄）（H₂PO₄）₂]}·10H₂O （9）（H₂en）12K2（H₂O）₂Na [H19K(P₄Mo₆O₃₁)₂]₂·6H₂O （10）[Cu（2,2’-bipy）]6[(PMoVI11MoVO₄₀)][（Mo6O22）]·H₂O （11）Both compounds9and10are composed of M[P₄Mo₆O₃₁]₂（M=K or Na）dimmers. In the basic structural unit of compound9, there are two Na[Mo6P4]₂dimers, each dimer and four adjacent {NaO6} are connected to forma one-dimensional chain. In compound10, both Na and K cobridge the dimer[Mo6P4]₂.It should be noted that there are two types of1D channels in compound10.Compound11is a1D chain composed of [Mo₈-6O₂₂]anion and[PMoVI11MoVO₄₀]4-anion clusters linked by [Cu（2,2’-bipy）]₂+complexes. The{Mo6} cluster in the1D long chain {Mo₆}-Ｃu-{PMo₁₂} is very rare. 4. A novel niobium-transition metal mixed complexes with1,10-phenanthrolinehas been synthesized:[Cu₂（phen）4（NbF₄）₂（μ-O）₂（μ-F）][NbF₆]（12）Compound12is composed of two Cu(C₁₂H₈N₂)₂O and two NbOF5complexesbridged by O and F atoms. The F atoms play a bridging role, which is rare. Thecompound is difficult to dissolve in water, and has relatively strong fluorescence, highthermal stability. Therefore, compound12could be a potentialsolid fluorescence emission material.更多还原