【作者】 鹿颖；

【导师】 王恩波；

【作者基本信息】 东北师范大学 ， 无机化学， 2005， 博士

【摘要】 本论文利用Keggin、Standberg、Wells-Dawson和Preyssler结构多金属氧酸盐簇为基本建筑单元,通过各种过度金属化合物或稀土化合物的修饰或桥连,构筑新型的多金属氧酸盐化合物,研究这类化合物的合成条件及规律,以及新物质结构和性能间的关系。利用水热技术和水溶液合成方法,合成了19种新型的多金属氧酸盐化合物,通过元素分析,IR,EPR,XRPD,TG和单晶X-射线衍射对晶体结构进行了表征,对化合物的热稳定性、磁学特性和荧光性质进行了初步研究。1.以Keggin结构多金属氧酸盐为建筑单元,通过过度金属化合物的修饰或连接,水热合成和结构表征了5种新型多金属氧酸盐化合物:[{PMo8V6O42}{Co(H2O)(2,2’-bpy)2}2][Co(2,2’-bpy)3]{PMo8V6O42}·6H2O (1)[{PMo8V6O42}{Cu(2,2’-bpy)}{Cu(2,2’-bpy)2}2]·3.5H2O (2)[4,4’-H2bpy]2[4,4’-Hbpy][PCuMo11O39]·H2O (3)[4,4’-H2bpy]2[4,4’-Hbpy][PZnMo11O39]·2.75H2O (4)[4,4’-H2bpy][Cu(4,4’-bpy)]2[HPCuMo11O39] (5)化合物1和2具有过度金属化合物支撑的多金属氧酸盐簇结构。化合物3和4是两个由过度金属取代的Keggin杂多钼酸盐构成的一维链化合物。化合物5显示了一个由多氧钼酸盐链{HPCuMo11O39}n4n-和过度金属配位聚合物链{Cu(bpy)}nn+相互连接形成的层状结构。此外,还得到了一种由α-Keggin多氧阴离子和铜磷酸盐阳离子[Cu4(2,2’-bpy)4(H2O)2(PO4)2]2+构成的杂化材料[Cu4(2,2’-bpy)4(H2O)2(PO4)2](H3O)-[PMo12O40] (6)。2.以Standberg结构多氧钼磷酸盐为建筑单元,通过过度金属化合物的修饰或连接,水热合成和结构表征了4种新型多金属氧酸盐化合物:(4,4’-H2bpy)0.5{[Ni(H2O)5][Ni(4,4’-Hbpy)(H2O)4][Mo5P2O23]} (7)(4,4’-H2bpy)0.5{[Co(H2O)5][Co(4,4’-Hbpy)(H2O)4][Mo5P2O23]} (8)[{Cu(im)4}2{H2Mo5P2O23}]·3H2O·(im) (9)[4,4’-H2bpy]2[{Cu(4,4’-bpy)2}Mo5P2O23]·4H2O (10)化合物7和8显示了新颖的双支撑的多金属氧酸盐簇结构,在化合物7和8中两个不同的过度金属化合物碎片[M(H2O)5]2+ (M = Ni, Co)和[M(4,4’-Hbpy)(H2O)4]3+ (M =Ni, Co)被支撑在[Mo5P2O23]6-簇上。化合物9也具有双支撑的多金属氧酸盐簇结构,两个相同的{Cu(im)4}2+碎片被支撑在[H2Mo5P2O23]4-簇上。并且,在化合物9的双支撑的多金属氧酸盐簇之间存在着弱的Cu…O作用,这种作用将相邻的双支撑的多金属更多还原

【Abstract】 The aim of this thesis is the synthesis of new polyoxometalate compounds on the basis ofKeggin, Standberg, Wells-Dawson and Preyssler type polyoxoanion clusters, which aredecorated or bridged by various transition metal compounds or rare earth compounds. Thestudy on synthetic conditions and rules for these new compounds and the exploration ofrelationships between structures and properties for these new compounds are also carried out.Nineteen new polyoxometalate compounds have been synthesized on the basis ofhydrothermal technique and/or water solution synthesis methods and structurallycharacterized by elemental analyses, IR, EPR, XRPD, TG and single crystal X-raydiffractions. The thermal stabilities, magnetic properties and fluorescent activity of thesecompounds have been studied.1. Five new polyoxometalate compounds on the basis of Keggin type polyoxoanioncluster have been hydrothermally synthesized and structurally characterized:[{PMo8V6O42}{Co(H2O)(2,2’-bpy)2}2][Co(2,2’-bpy)3]{PMo8V6O42}·6H2O (1)[{PMo8V6O42}{Cu(2,2’-bpy)}{Cu(2,2’-bpy)2}2]·3.5H2O (2)[4,4’-H2bpy]2[4,4’-Hbpy][PCuMo11O39]·H2O (3)[4,4’-H2bpy]2[4,4’-Hbpy][PZnMo11O39]·2.75H2O (4)[4,4’-H2bpy][Cu(4,4’-bpy)]2[HPCuMo11O39] (5)Compounds 1 and 2 exhibit transition-metal compound supporting polyoxometalatecluster structure. Compounds 3 and 4 show novel one-dimensional zigzag chains formed bytransition metal substituted Keggin heteropolymolybdate. Compound 5 possesses a noveltwo-dimensional network constructed from the interconnecting of polyoxomolybdate chains{HPCuMo11O39}n4n-and transition metal coordination polymer chains {Cu(4,4’-bpy)}nn+. Inaddition, [Cu4(2,2’-bpy)4(H2O)2(PO4)2](H3O)[PMo12O40] (6), a hybrid material based on[Cu4(2,2’-bpy)4(H2O)2(PO4)2]2+ and an α-Keggin polyoxoanion, has been prepared.2. Four new polyoxometalate compounds have been hydrothermally synthesized byvirtue of Standberg type polyoxoanion building units:(4,4’-H2bpy)0.5{[Ni(H2O)5][Ni(4,4’-Hbpy)(H2O)4][Mo5P2O23]} (7)(4,4’-H2bpy)0.5{[Co(H2O)5][Co(4,4’-Hbpy)(H2O)4][Mo5P2O23]} (8)[{Cu(im)4}2{H2Mo5P2O23}]·3H2O·(im) (9)[4,4’-H2bpy]2[{Cu(4,4’-bpy)2}Mo5P2O23]·4H2O (10)Compounds 7 and 8 exhibit novel bisupporting polyoxometalate cluster structure, wheretwo distinct transition metal complex fragments [M(H2O)5]2+ (M = Ni, Co) and[M(4,4’-Hbpy)(H2O)4]3+ (M = Ni, Co) are supported on the [Mo5P2O23]6-cluster. Compound9 also possesses bisupporting polyoxometalate cluster structure, where two {Cu(im)4}2+fragments are supported on the [H2Mo5P2O23]4-cluster. In compound 9, adjacent bisupportingdiphosphopentamolybdate clusters link to each other via the weak Cu…O interactiongenerating a uniform two-dimensional grid network. Compound 10 exhibits athree-dimensional framework with one-dimensional channels built from {Cu(4,4’-bpy)2}n2n+coordination polymer sheets pillared by [Mo5P2O23]6-clusters. The magnetic property forcompound 10 was studied and antiferromagnetic interactions exist in compound 10.3. Five new polyoxometalate compounds have been synthesized on the basis of lacunaryWells-Dawson anions decorated or connected by Ln3+ ions:KNa3[Nd2(H2O)10(α2-P2W17O61)]·11H2O (11)(H3O)[Nd3(H2O)17(α2-P2W17O61)]·6.75H2O (12)(4,4’-H2bpy)2[Nd2(H2O)9(α2-P2W17O61)]·4.5H2O (13)(4,4’-H2bpy)2[La2(H2O)9(α2-P2W17O61)]·4.5H2O (14)(4,4’-H2bpy)2[Eu2(H2O)9(α2-P2W17O61)]·5H2O (15)Compound 11 shows a bisupporting polyoxometalate cluster structure where two{Nd(H2O)7}3+ fragments are supported on the polyoxometalate dimer[{Nd(H2O)3(α2-P2W17O61)}2]14-, which represents the first bisupporting polyoxometalatecompound based on a polyoxometalate dimer. Compound 12 displays a one-dimensionalchain structure built up of bisupporting polyoxoanions [{Nd(H2O)7}2{Nd(H2O)3-(α2-P2W17O61)}2]8-and Nd3+ ions. Compounds 13-15 are isostructural, which show atwo-dimensional structure constructed of one-dimensional polyoxometalate chains[Ln(H2O)2(α2-P2W17O61)]n7n-linked by Ln3+ ions. Compounds 12-15 represent the firstcharacterized extended structure compounds formed by lacunary Wells-Dawson anions andtrivalent lanthanide ions. The fluorescent spectrum of compound 15 was measured, whichexhibits the characteristic transition of the Eu3+ ion.4. Four new polyoxometalate compounds on the basis of Preyssler type polyoxoanioncluster have been synthesized and structurally characterized:Na2[{Ce(H2O)8}4{Na(H2O)P5W30O110}]·12H2O (16)H4Na4[Nd2(H2O)14{Na(H2O)P5W30O110}]·22H2O (17)K2Na[Eu3(H2O)14(HNA)3{Eu(H2O)P5W30O110}]·3H2O (18)H2[Ce4(H2O)16(HNA)6{Na(H2O)P5W30O110}]·12H2O (19)Compound 16 exhibits a tetrasupporting polyoxometalate cluster structure where four{Ce(H2O)8}3+ fragments are supported on the [Na(H2O)P5W30O110]14-cluster. Compounds 17and 18 show a similar one-dimensional chain structure built from [Mn+(H2O)P5W30O110](14-n)-(Mn+=Na+ in 17, Eu3+ in 18) clusters linked by Ln3+ cations. Compound 19 has atwo-dimensional network constructed by one-dimensional [Ce2(H2O)10{Na(H2O)-P5W30O110}]n8n-chains and {Ce2(H2O)6(HNA)6}6+ linkers. Compounds 16-19 represent thefirst characterized modify or extended structure compounds based on Preyssler anions. Thefluorescent spectrum of compound 18 was measured, which exhibits the characteristictransition of the Eu3+ ion.更多还原