几个新型杂多钨酸盐的合成及晶体结构

【作者】 仝瑞占；

【导师】 薛岗林；

【作者基本信息】 西北大学 ， 物理化学， 2010， 硕士

【摘要】 本论文利用水热合成技术,通过含氮有机配体、抗衡离子及过渡金属离子的调变制备了九个新的杂多钨酸盐,并对这些化合物进行了元素分析、IR和单晶X-射线衍射表征,同时也对部分化合物的固态漫反射光谱性质、热稳定性、荧光光谱性质和磁学性质进行了研究。1.采用配体2,2’-联吡啶和1,2-环己二胺,合成了两例基于三缺位[AsW9O34]9-单元构建的有机-无机砷钨酸盐：H2[{Cu(2,2’-bpy)}8(H2O)2(AsW9O34)2]·12H2O(1)(NH4)3[Ni(C6H,4N2)2]3[Ni(C6H15N2)Ni(H2O)Ni2(AsW9O34)2]·3H2O(2)在化合物1中,两个三缺位多阴离子[a-AsW9O34]9-通过Cu3-O键桥连形成二聚结构,它是第一例基于[a-AsW9O34]9-阴离子的连接八个铜配合物的砷钨酸盐。化合物2是一例新的含有四核有机镍[Ni4(C6H15N2)(H2O)]单元的夹心型砷钨酸盐。2.采用不同的配体,合成了五例基于饱和Keggin离子构建的有机-无机多金属氧酸盐：[Co(2,2’-bpy)3]2[AsWⅤWⅥ11040]·3H2O(3)[Co(2,2’-bpy)3][HAsW12040]-8H2O(4)[Ni(C6H14N2)2]3[AsWⅤ3WⅥ9O40] (5)[4,4’-H2bpy]H[Co(imi)4(AsCo(imi)W11O39)](6)[Co(2,2’-bpy)3]1.5[Co(2,2’-bpy)2(H20)SiWⅤWⅥ11O40]·0.5H2O(7)化合物3,4和5中,不同数目的过渡金属络离子与Keggin离子间主要通过静电引力和氢键相互作用；在化合物6中,Co(imi)单取代Keggin离子的一个端氧向过渡金属络离子配位形成了Keggin离子单支撑的有机-无机杂化化合物,进而由金属配合物[Co(imi)4桥连相邻多阴离子形成一维链状结构；化合物7为饱和Keggin离子单支撑的有机-无机杂化化合物,进而通过氢键形成一维双股链状结构。3.以4,4’-联吡啶和咪唑为混配体,水热合成和结构表征了一例新型3D拓展结构的有机-无机Dawson型砷钨酸盐：Cu18(imi)4(bpy)6(H2O)[AsⅤ2WⅤ2WⅥ16O62]·2H2O(8)化合物8具有5-连接的氮化硼拓扑,拓扑符号为(46·64)。化合物8中多阴离子作为七齿无机配体与周围的七个过渡金属离子配位,显示了到目前为止修饰的Dawson型砷钨酸盐的最高连接。4.通过抗衡离子的调节,合成了一例铜取代的夹心型砷钨酸盐：Na(H2O)6Cu(H2O)4(NH4)6[Cu3.5(NH4)2(H2O)4(AsW9O33)2]·5H2O(9)化合物9的杂多阴离子为夹心型结构,两个[ASW9O33]9-建筑单元间含有一个新的[Cu3.5(NH4)2(H2O)4]中心单元,每个夹心型杂多阴离子均通过四个Cu-O-W键连接了与其相邻的四个多阴离子形成二维网络结构。更多还原

【Abstract】 In this paper, nine new polyoxometalates were synthesized under the hydrothermal conditions by adjusting organic N-donor ligands, counter ions and transition-metal ions, all of which were characterized by elemental analysis, IR and single crystal X-ray diffraction. Some of these compounds were characterized by UV-vis diffuse reflectance spectrum, fluorescent spectrum, thermal anelysis or magnetic measurement.1. Two new inorganic-organic tungstoarsenates on the basis of trivacant Keggin ion [ASW9O34]9- have been hydrothermally synthesized by using organic ligands 2,2’-bpy or 1,2-diaminocyclohexane:H2[{Cu(2,2’-bpy)}8(H2O)2(AsW9O34)2]-12H2O(1)(NH4)3[Ni(C6H14N2)2]3[Ni(C6H15N2)Ni(H2O)Ni2(AsW9O34)2]·3H2O(2)In compound 1, two trivacant polyanions [a-AsW9O34]9- are connected via Cu-O to form a centrosymmetric dimer, on which eight-copper-complexed were connected. Compound 2 is a new sandwich tungstoarsenate constructed from two trivacant polyanions [ASW9O34]9-linked through an unique [Ni4(C6H15N2)(H2O)] unit.2. Five new inorganic-organic hybrids based saturated Keggin or monosubtituted Keggin polyoxometaltates have been hydrothermally synthesized by using different organic ligands:[Co(2,2’-bpy)3]2[AsWⅤWⅥ11O40]-3H20(3)[Co(2,2’-bpy)3][HAsW12O40]-8H2O(4)[Ni(C6H14N2)2]3[AsWⅤ3WⅥ9O40] (5)[4,4’-H2bpy]H[Co(imi)4(AsCo(imi)W11O39)](6)[Co(2,2’-bpy)3]1.5[Co(2,2’-bpy)2(H2O)SiWⅤWⅥ11O40]-0.5H2O(7)In compounds 3,4 and 5, the main interactions between metal complexes and saturated Keggin ions are hydrogen bond and electrostatic interaction; compound 6 is a Co(imi) gruop monosubtituted Keggin compound, and further covalently connected by [Co(imi)4] units to a one-dimensional chain; in compound 7, the saturated Keggin ion coordinates to Co(2,2’-bpy)2(H2O)2+ to form a monosupporting hybrid, furthmore linked by hydrogen bond to a 1D chain structure.3. A novel inorganic-organic Dawson-type tungstoarsenate has been synthesized by introducing mixed organic ligands 4,4’-bpy and imidazole under the hydrothermal conditions and structurally characterized:CuI8(imi)4(bpy)6(H2O)[AsⅤ2WⅤ2WⅥ16O62]-2H2O(8)The compound 8 exhibits a five-connected boron nitride topology with the Schlafli symbol (46·64), in which Dawson polyanoin as hepta-dentate inorganic ligands coordinates with seven metal ions, representing the highest connecting number of modifying Dawson POMs.4. A new copper-substituted sandwich tungstoarsenate has been hydrothermally synthesized by adjusting different counter ions:Na(H2O)6Cu(H2O)4(NH4)6[Cu3.5(NH4)2(H2O)4(AsW9O33)2]-5H2O(9)Compound 9 consists of two [ASW9O33]9- moieties linked by a new [Cu3.5(NH4)2(H2O)4] unit, and it is connected to four neighbors via four Cu-O-W bonds to form 2D network structure.更多还原