【作者】 王君；

【导师】 杨国昱；

【作者基本信息】 北京理工大学 ， 化学， 2014， 硕士

【摘要】 本文依据文献，制备了系列三缺位钨-氧簇，包括K8Na₂[A-α-GeW₉O₃₄]·25H₂O，Na9[A-α-PW₉O₃₄]·7H₂O及Na10[A-α-SiW₉O₃₄]·24H₂O等。以这些缺位金属-氧簇为前驱体，采用水热法，探索合成了7个基于3d-4f异金属Fe-Ln （Ln=Sm、Ce）及过渡金属（Fe、Ni、Cu）取代的钨-氧簇。分子式如下：1、（enH₂）₁₃HK₉[Fe₆Sm₆（H₂O）₁₂(GeW₁₀O₃₈)₆]·42H₂O （en为乙二胺）2、（enH₂）₁₃H₃K₇[Fe₆Ce₆（H₂O）₁₂(GeW₁₀O₃₈)₆]·42H₂O3、（enH₂）₆K[HFe₆(B-α-GeW₉O₃₄)₂（α-GeW6O26）（H₂O）₂]·11H₂O4、（enH₂）₅[（enH₂）₂Fe4(FeW₉O₃₄)₂][（enH）₂Fe4(FeW₉O₃₄)₂]·9H₂O5、（enH₂）₁₁[{(B-α-PW₉O₃₄)Fe₃（OH）₃}4（PO₄）₄Fe]·38H₂O6、[Ni₆（μ₃-OH）₃（H₂O）₂（dien）₃(B-α-PW₉O₃₄)]·4H₂O （dien为二乙烯三胺）7、（enH₂）₂[（en）₄Cu₈（H₂O）₂(B-α-SiW₉O₃₄)₂]·8H₂O其中，化合物1是以K8Na₂[A-α-GeW₉O₃₄]·25H₂O为前驱体合成的一例基于[Sm–（μ₃-O）₃–Fe]桥和二缺位Keggin型[α-GeW₁₀O₃₈]12–簇单元构建的三聚体，K⁺填充在中心空穴处。该三聚体通过K⁺离子的联结作用形成六聚体，而六聚体间进一步通过K⁺的联结形成一维链状结构；化合物2的结构与化合物1类似，它是基于[Ce–（μ₃-O）₃–Fe]桥和二缺位的Keggin型[α-GeW₁₀O₃₈]12–单元构建的簇聚物链状结构；化合物3是一例六核铁取代的含有[B-α-GeW₉O₃₄]10–和[α-GeW6O26]12–混合金属氧簇单元的双夹心结构，K⁺离子将二个结构单元联结起来形成独特的环状结构，其中心填充着乙二胺分子。化合物1–3均是以K8Na₂[A-α-GeW₉O₃₄]·25H₂O为前驱体合成的含有金属铁的簇合物，其结构中K⁺离子的连接作用增加了结构的稳定性。化合物4和5是基于Na9[A-α-PW₉O₃₄]·7H₂O为前驱体合成的铁取代钨氧簇合物。其中，化合物4是基于Fe4(FeW₉O₃₄)₂三明治型簇阴离子单元构建的一维链状结构，夹心带中的四核铁氧簇为混合价态；化合物5是一个十三核Fe13簇取代的四聚体。化合物6是以Na9[A-α-PW₉O₃₄]·7H₂O为前驱体合成的镍氧簇取代的簇合物。化合物7是以Na10[A-α-SiW₉O₃₄]·24H₂O为前驱体合成的八核铜氧簇取代的簇合物。在化合物6和7的结构中，有机胺均参与配位形成有机-无机杂化结构。这些化合物分别通过红外光谱、元素分析、紫外光谱、热重分析、X-射线粉末衍射及X-射线单晶衍射等手段进行了表征，并对化合物1和3的磁性进行了研究，均表现出反铁磁相互作用。更多还原

【Abstract】 According to the literature, we prepared a series of tri-vacant tungsten-oxo clustes,such as: K8Na₂[A-α-GeW₉O₃₄]·25H₂O, Na9[A-PW₉O₃₄]·7H₂O, Na10[A-α-SiW₉O₃₄]·24H₂O,etc. Using these lacunary tungsten-oxo clusters as precursors, we succeeded in exploringfour classes of tungsten-oxo clustes that were substituted by Fe-Ln （Ln=Sm, Ce）3d-4fheterometallic systems, Fe, Ni and Cu. The formulas of these compounds are as follows:1、（enH₂）₁₃HK₉[Fe₆Sm₆（H₂O）₁₂(GeW₁₀O₃₈)₆]·42H₂O （en=1,2-ethylenediamine）2、（enH₂）₁₃H₃K₇[Fe₆Ce₆（H₂O）₁₂(GeW₁₀O₃₈)₆]·42H₂O3、（enH₂）₆K[HFe₆(B-α-GeW₉O₃₄)₂（α-GeW6O26）（H₂O）₂]·11H₂O4、（enH₂）₅[（enH₂）₂Fe4(FeW₉O₃₄)₂][（enH）₂Fe4(FeW₉O₃₄)₂]·9H₂O5、（enH₂）₁₁[{(B-a-PW₉O₃₄)-Fe₃（OH）₃}4（PO₄）₄Fe]·38H₂O6、[Ni₆（μ₃-OH）₃（H₂O）₂（dien）₃(B-α-PW₉O₃₄)]·4H₂O （dien=diethylenetriamine）7、（enH₂）₂[（en）₄Cu₈（H₂O）₂(B-α-SiW₉O₃₄)₂]·8H₂OAmong them, compound1was synthesized by using the K8Na₂[A-α-GeW₉O₃₄]·25H₂Oprecursor. It has [Sm–（μ₃-O）₃–Fe] bridges and a trimeric cryptand-type[KFe₃Sm3（H₂O）₆(α-GeW₁₀O₃₈)₃]17-aggregate that contains three divacant Keggin[α-GeW₁₀O₃₈]12-subunits. A K⁺embedded in the central. What’s more, under the couplingeffect of K⁺, two trimmers aggregated into hexamers and the hexamers aggregated into a1-D chain. The structure of the compound2is similar to compound1. It’s a trimericcryptand-type structure that include the [Sm–（μ₃-O）₃–Fe] bridges and the Keggin type[α-GeW₁₀O₃₈]12-subunits. It also presented a1-D chain-like structure. Compound3is anexample of double sandwich structure which was substituted by two Fe₃clusters. Thepolyoxometalates it contains are two [B-α-GeW₉O₃₄]10-fragments and one [α-GeW6O26]12-.Two double sandwich structural units are interconnected with each other via two K⁺cations,giving rise to a ring-like assembly. The common futures of compounds1-3are as follows:（a） they all made by using the same precursor, K8Na₂[A-α-GeW₉O₃₄]·25H₂O.（b） they allsubmitted by transition metal, Fe.（c） the K⁺embedded in these three structures, and thestructures of them became more stable. The compounds4and5are both synthesized basedon the Na9[A-PW₉O₃₄]·7H₂O precoursor and substituted by irons clusters. The compound4is contained the [B-α-FeW₉O₃₄]11-fragment with the1-D chain-like assembly. The ironclusters in the central belt have the mixed valence. The compound5is a tetra-polymeric structure containing Fe13clusters. A Fe4disordered in four sites of the central cube. Thecompounds6is a Ni substituted polymer synthesized by using the Na9[A-PW₉O₃₄]·7H₂O.The compound7is a Cu substituted fragment. However, the precursor used in it isNa10[A-α-SiW₉O₃₄]·24H₂O. In the structures of compounds6and7, they both belongs tothe organic-inorganic hybrid structures with the coordination of the organic amines. In thefollowing works, these seven compounds were structurally characterized by usingsingle-srystal X-ray diffraction, powder X-ray diffraction （PXRD）, thermogravimetric （TG）analyses and elemental analyses. The magnetic susceptibility measurements demonstratethe presence of antiferromagnetic interactions in compounds1and3.更多还原