【作者】 赵卫锋；

【导师】 张联盟； 靳素荣；

【作者基本信息】 武汉理工大学 ， 材料学， 2005， 硕士

【摘要】 多金属氧酸盐因其丰富的结构及其独特的性质在功能催化、生物制药、薄膜材料、电工器件及磁学等领域有着广泛的应用前景。这类化合物的设计与制备将成为推动化学科学及其相邻学科发展的新动力。 本文采用中温水热合成技术,使用简单原料,通过调节反应条件和有机模板剂合成了两种磷钼多金属氧酸盐:{[Cu（phen）₂][Cu（phen）（OH₂）]₂[P₂Mo₅O₂₃]}·9H₂O和（H₃dien）₂P₂Mo₅O₂₃;两种磷钨多金属氧酸盐[Cu（2,2-bipy）（OH₂）₂][Cu（2,2-bipy）]₂（PO₄）)₂(P2W₁₈O₆₂)₍0.5·2H₂O和（enH₂）₅(HP₂W₁₈O₆₂)₂·22H₂O。利用ICP,CHN,IR,TG-DTA及单晶X-ray衍射等测试手段研究了它们的组成、晶体结构及性质,并初步探索了影响多金属氧酸盐骨架的因素。 实验发现,原料配比和pH值对晶体产物的生成结果有重要影响,同时第二金属种类和有机模板剂的结构是产物生成中至关重要的因素,不同有机胺分子将导致不同结构的产生。 研究结果表明化合物{[Cu（phen）₂][Cu（phen）（H₂O）]₂[P₂Mo₅O₂₃]}·9H₂O是以Strandberg结构杂多阴离子簇为主要结构新型化合物。杂多阴离子[P₂Mo₅O₂₃]^6-由五个MoO₆八面体和两个PO₄四面体构成,形成了一个变形五角双锥结构,并配位于第二金属铜离子的氨基配合物上,通过phen基团的非键π-π堆积作用构成具有层状结构的多金属氧酸盐-有机杂化材料。通过改变有机模板剂得到了另一种Strandberg结构多金属氧酸盐（H₃dien）₂P₂Mo₅O₂₃,该化合物中质子化的有机胺阳离子通过多点氢键及静电引力与杂多阴离子作用,并平衡骨架负电荷。 磷钨多金属氧酸盐{[Cu（2,2-bipy）（OH₂）₂][Cu（2,2-bipy）]₂（PO₄）}₂-(P₂W₁₈O₆₂)·2H₂O是基于Dawson结构杂多阴离子的多金属氧酸盐-有机杂化分子,该化合物中三个不同的Cu配阳离子与杂多阴离子通过W（1）-O（2）-Cu（1）-O（32）-P（2）-O（34）-Cu（1A）-O（1A）-W（1A）桥交替排列形成一种新颖孔道结构。由于有机结构导向剂的结构变化,在化合物（enH₂）₅(HP₂W₁₈O₆₂)₂·22H₂O中,杂多阴离子与质子化的有机胺通过氢键作用连接为相互平行链,相邻链之间通过N-H…O键作用形成二维层状结构。更多还原

【Abstract】 Due to it’s rich structure types and special functions, Polyoxometalates have potential and extensive application in catalysis, biology, medicine, thin film material, electrician and magnetics etc.. The design and synthesis of metal oxide heterpoly compound will accelerate the develop of chemistry and other research areas related.In this research, two novel molybdophosphates {[Cu(phen)2][Cu(phen)(OH2)]2 [P2MO5O23]}9H2O, (H3dien)2P2Mo5O23 and two novel tungstophosphates [Cu(2,2-bipy)(OH2)2] [Cu(2,2-bipy)]2(PO4)(P2W18O62)0.5 2H2O, and (enH2)5 (HP2W18O62)2 22H2O organic-inorganic hybrid compounds were hydrothermally synthesized respectively by modifying synthetic conditions and using simple starting materials and organic amines as templates. The structures and properties of these composites were determined by single crystal X-ray diffraction, ICP, CHN, IR and TG-DTA. The influencing factors on Mo-P and W-P framework of hybrid compound were also studied prelimimarily.It was found that both the pH value and starting material quotas of the reaction system affect the final production greatly. The species of the second metal and the species of the organic templates are two key factors for the production. Different organic amines can result in different structure.The results showed that {[Cu(phen)2][Cu(phen)(OH2)]2[P2Mo5O23]}-9H2O and (H3dien)2P2Mo5O23 have the same Strandberg molybdophosphate heteropolyanions structure as that of the mail inorganic structure. The Strandberg type heteropolyanions [P2M5O23]6- was composed of five MoO6 octahedra and two PO4 tetrahedrons, which showed a distorted pentagonal bi-pyramidal configuration, and bonded to the second metal amidocyanogen copper cation. The compound was a polyoxometalates-organic hybrid material with samdwich structure through π-π stacking interactions between phen groups. The compound (H3dien)2P2Mo5O23 showed an infinite planar structure by hydrogen bonds between polyanion [P2Mo5O23]6- and protonated [dienH3]3+. The protonated dien occupied the interlayer of the framework and balanced the charge of the framework.The compound [Cu(2,2-bipy)(OH2)2][Cu(2,2-bipy)]2(P04)(P2W18O62)0.5 2H2O was polyoxometalate-organic hybrid material based on Dawson type heteropolyanions. It indicated an unprecedented straight channels formed by three different copper-amine cationic units through W(1)-O(2)-Cu(1)-O(32)-P(2)-O(34)-Cu(1A)-O(1A)-W(1A) chain. In the inorganic-organic hybrid materials (enH2)5(HP2W18O62)2 22H2O, the heteropoly anions and protonated enH22+ were built into a double parallel chains by hydrogen bonds. The adjacent chains formed a 2D planar structure by N-H.. .O hydrogen bonds.更多还原