节点文献
新型多酸超分子化合物的合成、结构和性质研究
Synthese, Structures, and Properties Study of Novel Supramolecular Compounds Based on Polyoxometalates
【作者】 李允伍；
【导师】 王恩波；
【作者基本信息】 东北师范大学 ， 无机化学， 2009， 硕士
【摘要】 本论文选用各种类型的多金属氧酸盐为基本构筑单元,与大阳离子簇以及金属-有机化合物通过超分子作用力或配位键来构筑新型的多金属氧酸盐超分子组装体;同时选取不同配位能力的3d、4f金属离子以及具有各种空间构型的有机配体来构筑新型高维的金属氧簇超分子网络,研究新型超分子化合物的合成条件及规律,考察配体的几何构型,辅助配体对于整个结构的影响等规律,以探究分子自组装原理,以及新物质结构和性能间的关系。利用水热技术和常规水溶液合成方法,合成了9个新型的基于多金属氧酸盐和3d、3d-4f金属氧簇构筑的高维超分子化合物,通过元素分析,IR,UV-Vis,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.利用不同的多金属氧酸盐和金属-有机阳离子作为建筑块,得到3个基于多金属氧酸盐的超分子化合物,并对影响晶体空间堆积的各种因素进行了探讨。其中化合物1是一个由循环三聚的Dawson型多酸[P2W16Mn2O60]324-和3d-4f杂核阳离子簇[Ce3Mn2O6（OAc）6（H2O）9]2+所组成的离子晶体型超分子化合物,其中循环三聚的Dawson型多酸代表着一种新的Dawson型多酸的连接方式,同时,化合物1也是第一例基于多酸和3d-4f杂核阳离子簇的超分子化合物。化合物2是由β-[Mo8O26]4-同多阴离子和MnIII-希夫碱共同构筑的超分子组装体,在化合物2中,多酸层和金属-希夫碱层交替排列,通过静电力和范德华力形成3D的超分子化合物,它把古老的金属-希夫碱领域和多酸这个热点领域有机的结合在一起。化合物3是由仲钨酸[H2W12O42]10-通过过渡金属离子CuII连接而成的3D （8,3）-连接的纯无机拓扑网络。Na20[CeIV3MnIV2O6（OAc）6（H2O）9]2[P2W16MnIII2O60]3·21H2O （1） [N（CH3）4]2[Mn（Salen）（DMF）2]2[β-Mo8O26]·2DMF （2） KNa3[Cu（H2O）2{Cu（H2O）3}2(H2W12O42)]·16H2O （3）2.利用水热合成技术,通过合理的选用或者原位合成不同的有机配体和不同的过渡金属离子或稀土金属离子,采用分子识别和自组装原理成功的合成了6个新型高维金属氧簇超分子网络化合物。并且初步分析了不同金属离子的配位方式,配体的长度、柔韧性,以及混合配体对这些化合物的形成所产生的影响。化合物4-5是以对苯二氰为主体配体,通过加入不同功能的辅助配体,调节使其发生原位反应,从而得到2个新颖的拓扑网络。其中化合物4是通过具有1D梯状结构的2D超分子层发生平行互穿,形成的3D组装体。化合物5展现出由2D的波浪层构成的3D倾斜互穿结构。化合物6-9同时选用混合配体和混合金属,利用阴离子的模板效应,获得了4个3d-4f杂核的具有阳离子3D骨架的主客体超分子化合物。[Ni2（TP）2（BPP）2（H2O）2]n （4） {[Co（TP）（BPP）]4·6H2O}n （5） [Ln2（1,2-bdc）2（H2O）2Cu（inic）2]（ClO4） （Ln = Eu （6）, Tb （7）, Nd （8） , Sm （9））
【Abstract】 In this thesis, three novel polyoxometalate （POM） supramolecular assemblies based on macrocations clusters, metal-organic compounds and polyoxometalates have been synthesized via supramolecular interaction and coordination bonds. Moreover, a new series of high dimensional metal—oxogen clustes supramolecular networks have also been synthesized by choosing various of 3d or 4f metal ions with different coordination capacities and organic ligands with different space configuration. The study on synthetic conditions and rules for these new compounds, the effect of various auxiliary ligands on the ultimate structures, topological analyses, the principle of molecular self-assembly, and the exploration of relationships between structures and properties for these new compounds are also carried out.Nine new polyoxometalate and high dimensional metal—oxogen clustes supramolecular compounds have been synthesized on the basis of hydrothermal technique and/or convenient aqueous solution synthesis methods and structurally characterized by elemental analyses, IR, UV/Vis spectrum, XRPD, TG and single crystal X-ray diffractions. The thermal stabilities, magnetic properties and fluorescent activity of these compounds have been studied.1. Three new supramolecular compounds based on polyoxometalates and metal-organic cations building blocks have been synthesized and structurally characterized. We have also discussed the influence of various important factors to the cluster packing style. Among these compounds, compound 1 is the first ionic crystal supramolecular assembly base on unusual triple-Dawson-type polyoxoanions [P2W16MnIII2O60]324- and bipyramid-like 3d-4f heterometallic clusters [CeIV3MnIV2O6（OAc）6（H2O）9]2+. Compound 2 represents a new and rare supramolecular example constructed by MnIII-salen Schiff-base building blocks andβ-octamolybdate isopolyoxoanions, which combines POMs chemistry and Schiff-base chemistry two interesting fields together to prepare new hybrid materials. Compound 3 represents the first example of a pure inorganic 3D （8,3）-connected structural topology based on the [H2W12O42]10- building blocks and CuII linkers. Na20[CeIV3MnIV2O6（OAc）6（H2O）9]2[P2W16MnIII2O60]3·21H2O （1） [N（CH3）4]2[Mn（Salen）（DMF）2]2[β-Mo8O26]·2DMF （2） KNa3[Cu（H2O）2{Cu（H2O）3}2(H2W12O42)]·16H2O （3）2. Six new 3d or 3d-4f high dimensional metal—oxogen clustes supramolecular networks have been successfully synthesized by rational selecting and in situ ligands synthesize new organic ligands and different 3d or 4f metal ions on the basis of hydrothermal technique. We further study the effect of various of metal ions with different coordination capacities, the length and flexility of organic ligands, and mixed ligands on the ultimate structures of these compounds. Compounds 4-5 are modulated synthesize by introduction of various auxiliary ligands into an in situ ligands synthesis system of terephthalonitrile. Compound 4 contains a new type of 1D zigzag ladders, which are further interlocked with the other two identical ones, forming a 3D polycatenated framework. Compound 5 displays a new 3D‘‘inclined’’interpenetration architecture based on 2D undulated layers. Compounds 6-9 are four new anion-templated 3D heterobimetallic host-guest supramolecular assemblies based on the lanthanide-carboxylate layers and copper（I）-inic pillars. [Ni2（TP）2（BPP）2（H2O）2]n （4） {[Co（TP）（BPP）]4·6H2O}n （5） [Ln2（1,2-bdc）2（H2O）2Cu（inic）2]（ClO4） （Ln = Eu （6）, Tb （7）, Nd （8） , Sm （9））