【作者】 崔继文；

【导师】 徐吉庆；

【作者基本信息】 吉林大学 ， 无机化学， 2008， 博士

【摘要】 本论文主要研究金属-氧簇合物的合成、结构和性能,旨在合成出具有新颖结构的金属-氧簇合物及簇聚物,探讨合成条件对合成结果的影响,并研究其相关性能。1.合成了三个新的Keggin结构钨-钒-氧簇合物和四个新的Keggin结构钼-钒-氧簇合物（第三章）,其中化合物1是首例单帽单支撑的Keggin结构钨-钒-氧簇合物。化合物2是首例以Keggin结构钨-钒-氧簇为构筑单元,通过新颖的四核铜簇[Cu₄（2,2’-bipy）4（H₂O）2（PO₄）₂]₂+桥连而成的簇聚物。化合物3的不对称单元中含有两个[PW2V10O40（VO）2]11-簇阴离子,这是首例钒的含量大于钨的钨-钒-氧簇;其中一个簇阴离子与两个[Cu（2,2’-bpy）2H₂O]2+配合物阳离子以共价键相连接而成二支撑结构,这种结构类型的钨-钒-氧簇也是首次被发现。化合物4和5是罕见的具有三支撑分立结构的钼-钒-氧簇合物。化合物6是在一个不对称单元中包含两个簇阳离子的二帽Keggin结构钼-钒-氧簇合物。化合物7是少见的具有六帽Keggin结构的钼-钒-氧簇合物,在经典Keggin结构钼-氧簇阴离子[PMo12O40] 3-上帽合六个（VO）基团而构成。2.合成了四个新的Keggin结构钨-氧簇合物和两个新的钼-氧簇合物（第四章）,化合物8和11是具有二支撑结构的钨-氧簇合物,而化合物8又通过K+桥连成一维链状结构。化合物9和10都是经典Keggin结构钨-氧簇合物,其中化合物10同时含有经典Keggin结构和pseudo-Keggin结构两种类型的簇阴离子。化合物12是具有经典Keggin结构的钼-氧簇合物,并且通过氢键作用形成一维超分子链状结构。化合物13是具有二帽Dawson结构的分立砷-钼-氧簇合物。3.合成了两个钒-氧簇合物（第五章）,化合物14和15是以钒-氧簇为结构单元,与过渡金属配合物阳离子相连成为多金属环状结构,然后通过桥氧连接而成的二维簇聚物。4.对所合成的化合物进行了元素分析,红外光谱、光电子能谱和电子顺磁共振等多种谱学表征,研究了主要化合物的热稳定性和磁学性能,为进一步探索化合物功能特性与结构的关系提供了物质基础。更多还原

【Abstract】 Polyoxometalates （POMs） represent a fascinating class of inorganic chemistry with a structural variety and interesting properties, which are of use in fields as diverse as catalysis, sorption, molecular electronics, medicine, etc. As the applications of hydrothermal technique on the syntheses, various organic-inorganic hybrid materials of particular properties emerges constantly and much attention has been caused on the performances studies of various materials. In this field, an important advance is to decorate well-known polyoxoanions with various organic and/or transition metal complex moieties and then to link them up into one-, two-, even three-dimensional extended solid materials in appropriate ways. The introduction of metal complex can not only enrich the frameworks of polyoxometalates but also ameliorate their electronic and mangnetic properties. Based on this mechanism, we synthesized some non-classical metal-oxygen clusters, the cluster-polymers based on tungsten-vanadium and molybdenum- vanadium oxygen clusters. On the bases of X-ray structural analyses, some central compounds have been characterized by IR, XPS spectra. The thermal analyses and magnetic properties of some compounds have been studied, which would take an important role in the explorations of structures and functions for the compounds. I Keggin-structure tungsten-vanadium oxygen clustersApplying in hydrothermal synthesis reactions, we synthesized three Keggin-structure tungsten-vanadium oxygen clusters. [Ni（2,2’-bipy）3]1.5{PW10.79 V1.21O40（VO）0.5[Ni（2,2’-bipy）2L]}·0.5H₂O 1, [Cu₄（2,2’-bipy）4（H₂O）2（PO₄）2]H6.5[P W8.36V3.64O40]·2H₂O 2, [Cu（2,2’-bipy）3]2H14{PW2V10O40（VO）2[Cu（2,2’-bipy）2 H₂O]2}[PW2V10O40（VO）2]·10H₂O 3. Compound 1 is composed of the {PW10.79V1.21 O40（VO）0.5[Ni（2,2’-bipy）2L]}3-, which is further linked into a novel dimer through hydrogen bonging. Compound 2 is composed of an unusual Keggin [PW8.36V3.64 O40]4- cluster and a novel transition metal complex [Cu₄（2,2’-bipy）4（H₂O）2 （PO₄）2], which has 1D chain structure, is based on the Keggin structure tungsten-vanadium cluster [PW8.36V3.64O40]4- linked by [Cu₄（2,2’-bipy）4（H₂O）2（PO₄）2]. The sturucture of compound 3 features a novel 2D supramolecular layer built from the bicapped Keggin [PW2V10O40（VO）2]11- anions are decorated with [Cu（2,2’-bipy）2H₂O]2+ unit and the discrete bicapped Keggin [PW2V10O40（VO）2]11- anions having a high V/W ratio. The X-ray single crystal analysis, elemental analysis, IR, XPS and TG etc., have been performed on these compounds. Variable-temperature magnetic susceptibility measurements reveals the feature of ferromagnetic exchange of compound 1 and the feature of antiferromagnetic exchange of compounds 2 and 3.II Keggin-structure molybdenum-vanadium oxygen clustersApplying in hydrothermal synthesis reactions, we synthesized four Keggin- structure molybdenum-vanadium oxygen clusters. [Cu（2,2′-bipy）][Cu（2,2′-bipy）₂]₂ [PMo8V6O42]·1.5H₂O 4, [Cu（2,2′-bipy）][Cu（2,2′-bipy）₂]₂[PMo8V6O42]·2H₂O 5, [Co（2,2’-bipy）3]2{PMo12O40（VO）2[Co（2,2’-bipy）2（H₂O）]2}[PMo12O40（VO）2]·{（OH）10} 6, [PMo12V6O46]{（OH）9}·7H₂O 7. Compounds 4 and 5 feature a bi-capped keggin molybdenum-vanadium polyoxoanion, which is further interconnected with [Cu（2,2′-bipy）]2+ and [Cu（2,2′-bipy）₂]₂+ groups via the terminal oxygen atoms of polyoxoanions to form a tri-supported unit. Compound 6 features a bi-capped keggin molybdenum-vanadium polyoxoanion, which is further interconnected with [Co（2,2’-bipy）2（H₂O）]2+ groups via the terminal oxygen atoms of polyoxoanions to form a bi-supported unit. Compound 7 is decorated with six （VO）2+ based on the [PMo12O40]3-. The X-ray single crystal analysis, elemental analysis, IR, XPS and TG etc., have been performed on these compounds. Variable-temperature magnetic susceptibility measurements of compounds 4 and 5 reveal the feature of ferromagnetic exchange.III Keggin-structure tungsten oxygen clustersApplying in hydrothermal synthesis reactions, we synthesized four Keggin- structure tungsten oxygen clusters. K[PW12O40[Ni（1,10-phen）2（OH）]2]·2H₂O 8, （4,4′-bipy）4H3[PW12O40]·6H₂O 9, （4,4′-bipy）8H9[P1W12O40]2[P1W12O40]·10H₂O 10, [SiW12O40[Co（1,10-phen）2（H₂O）]2]·3H₂O 11. Compound 8, which has 1D chain structure, is based on the bi-supported Keggin structure tungste cluster [PW12O40 [Ni（1,10-phen）2（OH）]2]- linked by the alkali metal ion K+ bridges. Compounds 9 and 10 are compounds, which are composed of the classical keggin polyoxoanion [PW12O40]3- and the 4,4′-bipy units. Compound 11 features a keggin molybdenum polyoxoanion [SiW12O40]3-, which is further interconnected with [Co（1,10-phen）2 （H₂O）]2+ groups via the terminal oxygen atoms of polyoxoanions to form a bi-supported unit. The X-ray single crystal analysis, elemental analysis, IR, XPS and TG etc., have been performed on these compounds. The magnetic behavior of compound 8 was measured, and these data between 50 K and 250 K is coincident with the Curie-Weiss law, the Weiss Constant is big than zero, which indicates the presence of ferromagnetic interaction between the metal ions of them. Unfortunately, it is too difficult to fit the experimental mangentic data of these hetero-polymetallic spin systems using a suitable theoretical model.IV molybdenum oxygen clustersApplying in hydrothermal synthesis reactions, we synthesized two molybdenum oxygen clusters. [Ni（1,10-phen）3]2[PMo12O40]·2H₂O 12, （4,4′-bipy） [As2Mo18O62As2]·3H₂O 13. Compound 12 is composed of the classical keggin polyoxoanion [PMo12O40]3- and the transition metal complex units [Ni（1,10-phen）3]2+. The polyoxoanions of Compound 13 is decorated with two （AsO） unit based on the classical Dawson polyoxoanion [As2Mo18O62]3-. The X-ray single crystal analysis, elemental analysis, IR, XPS and TG etc., have been performed on these compounds.V vanadium oxygen clustersApplying in hydrothermal synthesis reactions, we synthesized two vanadium oxygen clusters. [Cu（2,2’-bipy）₂]₂[（V3O8.5）2] 14, [Zn（2,2’-bipy）]2[（V4O10.5）2] 15. Compound 14 exhibits an interesting 2D framework based on [（V3O8.5）2]4-. Compound 15 features a 2D network built from [（V4O10.5）2]4-. The X-ray single crystal analysis, elemental analysis, IR, XPS and TG etc., have been performed on both two compounds. The magnetic behavior of compound 14 was measured, and the data indicates the existence of ferromagnetic coupling of eleven V（IV） and three Ni（II） ions.更多还原