【作者】 张修堂；

【导师】 姜建壮；

【作者基本信息】 山东大学 ， 无机化学， 2008， 博士

【摘要】 由于同多酸或杂多酸化合物不仅具有丰富的拓扑结构，而且在吸附、催化、导电、能量存储、光学材料和主客体化学等领域中具有重要的应用价值。因此，同多酸或杂多酸化合物的合成与制备成为近十年来研究的重要领域之一。通过溶剂热和传统的溶液法，成功地合成出了十八个结构新颖的三维杂多酸化合物。通过元素分析、红外和TGA等进行了表征，同时对部分化合物的EPR和变温磁化率进行了测定。论文工作概述如下：1．简要的概述了近年来同多酸或杂多酸类化合物的最新研究发展动态，并归纳和总结了部分具有代表性化合物的结构类型、性能以及应用等。2．通过铝离子的诱导作用，合成了系列含稀土离子的三维结构化合物H₂{K（H₂O）₂Ln（H₂O）₅[H₂M₁₂O₄₂])·nH₂O（Ln=La，Sm，Eu,Gd，Tb，Dy,Ho，Er,Yb，Lu；M=W or W／Mo）（1-10）。该类化合物具有非常漂亮的结构构型，并且表现出了稀土离子双核结构间的顺磁性相互偶合作用。3．三个含锰（Ⅱ）离子的三维杂多酸化合物的合成以及结构、磁性、ESR和TGA的描述和表征。通过铝离子的诱导作用，合成了化合物H_22．5K₂Mn_1．5W_5．65Mo_1．35O₃₄Cl_1．5（XI）；而利用SeO₃^2-离子的诱导作用，却得到了具有不同结构的化合物H₅₉NaK₂Mn₂W_9．52Mo_2．48O₆₈Cl₂（Ⅻ）；在不加诱导离子的情况下，得到H₃₁Mn₂NaO₃₆W₆（ⅩⅢ）。4．引入有机配体3-（2-Pyridyl）pyrazol，利用水热法得到了五个含有第一过渡金属离子锰、铁、钴、镍和锌的三维结构化合物：[H₂（MnL₂）Mo₃O₁₀]_n（ⅩⅣ）、[H₂（FeL₂）Mo₃O₁₀]_n（ⅩⅤ）、（HL）{H₄[Co（L）₂]₂Mo₂O₈]}（H₂O）₃（ⅩⅥ）、[H₂（NiL₂）Mo₃O₁₀]_n（ⅩⅦ）、和H₄[Zn₂（L）₄]₂Mo₈O₂₆]（ⅩⅧ）。化合物（ⅩⅣ）、（ⅩⅤ）和（ⅩⅦ）拥有类似的一维链状结构[H₂（ML₂）Mo₃O₁₀]。在氢键的连接作用下，形成三维空间结构。通过诱导离子Al³⁺和SeO₃^2-离子作用，杂多酸的亚结构单元经过重新自组装后，通过和稀土离子或第一过渡金属离子的连接，得到三个系列十八个新颖的化合物。某些离子对杂多酸亚结构单元的诱导重组作用的研究还仅仅是个开始，我们在以后的研究中，将继续努力完善和深入这方面的工作。同时，我们首次将有机配体3-（2-Pyridyl）pyrazol引入了杂多酸的溶剂热合成，以后，我们将继续深入这方面的工作。更多还原

【Abstract】 The design of polyoxometalate clusters has attracted long-lasting research interest not only because of their appealing structural and topological novelty but also due to their unusual optical, electronic, magnetic, and catalytic properties, as well as their potential medical application due to their antiviral and inhibition of angiogenesis. Enighting novel compounds have been synthesized by the hydrothermal or conventional solution synthetic method in this thesis, which have been further characterized by X-ray single crystal diffraction and spectroscopes. Their single crystal molecular structures, as well as the magnetic properties for some compounds have also been systematically investigated. The major work of this thesis are outlined as following:1. In the first charter, the recent development of the iso- or heterometallates and the hybrid materials is reviewed. Some representative structures and applicable properties are also summarized.2. In the second charter, we describe the synthesis of a series of novel polyoxo（mixed-metalate） （W/Mo） compounds connected via trivalent lanthanide cations, namely H₂{K（H₂O）₂Ln（H₂O）₅[H₂M₁₂O₄₂]}·nH₂O （Ln = La, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb. Lu; M = W or W/Mo） （Ⅰ-Ⅹ）, with three dimensional framework. Their single crystal molecular structures, as well as the magnetic properties for compoundsⅡandⅣ-Ⅺ, have also been systematically investigated.3. In the third one, we describe the synthesis of three novel tungstate-molybdenum polyoxometalate compounds, namely H_2.5K₂[Mn_1.5W_5.65Mo_1.35O₂₄（H₂O）₄]Cl_1.5·6（H₂O） （Ⅺ）. H₅K₂Na[Mn₂（H₂O）₆(H₂W_9.52Mo_2.48O₄₂)]Cl₂·20（H₂O） （Ⅻ）, and Na₂[Mn₄（H₂O）₁₄(H₂W₁₂O₄₀)]·16H₂0 （ⅩⅢ）. Single crystal X-ray diffraction analysis results reveal their three-dimensional structural networks connected via divalent manganese cations with the help of potassium cations. Their magnetic characteristics were also systematically investigated.4. In the final part, five novel polyoxomolybdate compounds linked by divalent transitional metal cations coordinated with 3-（2-Pyridyl）pyrazole ligand, [H₂（ML₂）Mo₃O₁₀]_n （M = Mn （ⅩⅣ）, Fe （ⅩⅤ）, Ni （ⅩⅦ））, （HL）{H₄[Co（L）₂]₂Mo₂O₈]}（H₂O）₃ （ⅩⅥ）, H₄[Zn₂（L）₄]₂Mo₈O+（26）] （ⅩⅧ） （HL = 3-（2-Pyridyl）pyrazole） were designed and synthesized by the hydrothermal syntheses in the mixed ethanol/water solution. X-ray diffraction analyses reveal that compoundsⅩⅣ,ⅩⅤandⅩⅦconsists of one-dimensional wave-like chains built up from the asymmetric mixed-metalate building blocks of [H₂（ML₂）Mo₃O₁₀]. CompoundⅩⅥis bimetallic tetranuclear cluster constructed from corner-sharing {MoO₄} in which two Cu（Ⅱ） ions are further coordinated with four N atoms from two L" ligands and two bridging oxygen atoms exhibting distorted octahedron. Whereas, compoundⅩⅧis composed of two seperately parts with the dinuclear Cu₂（L）₄ andε-[H₄Mo₈O₂₆] unit.更多还原