【作者】 邱云峰；

【导师】 许林；

【作者基本信息】 东北师范大学 ， 无机化学， 2006， 硕士

【摘要】 本论文旨在依据分子设计的思想,通过选择不同的多酸主体建筑块和过渡系金属或有机分子,利用DCC方法,常规水溶液合成和水热合成技术,将多金属氧簇和过渡系金属或有机配体以共价键的方式相结合,合成具有一定功能性质的稳定的多金属氧簇官能化衍生物。并对它们电子性质、荧光性质、氧化还原电化学性质和电催化性质等作了较为系统的研究。化合物的分子式为:（Bu₄N）₂[Mo₆O₁₇（NAr）₂] [Ar = 2,6-（CH₃）₂C₆H₃] （1）（phen）₂[Cu₂（ac）₂（H₂O）₂(CrMo₆H₆O₂₄)]·10H₂O （2）Na₃（Himi）（imi）( NiMo₆H₆O₂₄)·H₂O （2） , （3）Na₂[Cu₃（OH）₄（H₂O）₄][β–Mo₈O₂₆]·13H₂O （4）[Co（H₂O）₅]₄[ Co（H₂O）₄][H₃O]₂[Mo₇O₂₄]₂·18H₂O （5）Na[Cu（imi）₂]₇[As₂W₁₈O₆₂]·5 H₂O （6）[Cu（CH₃-imi）₂]₅[AsW₁₂O₄₂]·2 H₂O （7）[Cu（CH₃-imi）₂]₅[PW₁₂O₄₂]·2 H₂O （8）[Cu（CH₃-imi）₂]₅[H₂W₁₂O₄₂]·2 H₂O （9）[Ag（imi）₂]₅[PW₁₁O₃₉Co（imi）]·3 H₂O （10）化合物1是利用DCC脱水制备二取代六钼酸盐有机亚胺衍生物的方法成功合成的,标题化合物对有机胺类的荧光具有有效的淬灭作用。化合物2和3是在常规水溶液中合成,结构上都展现了1D孔道的特点。化合物4和5是在常规水溶液中合成,是具有3D结构共价键键连的无机复合物。对亚硝酸根和双氧水具有较好的电催化还原作用。化合物6-10是水热合成的产品,他们是相同系列的化合物。值得说明的是,在标题化合物10的结构中,考虑超分子相互作用的情况下,由Ag（imi）₂^-金属配合物形成的阳离子2D层被[PW11O39Co（imi）]n5n-阴离子1D链沿着b轴方向垂直互穿。据我们所知这是第一例此类多酸阴离子1D链穿插金属配合物阳离子2D层结构的报道。标题化合物在208nm波长的激发下展示了较强的蓝光（λ= 469 nm）,有望成为潜在的荧光发射材料。本论文得到的化合物均不溶于水和常见的有机溶剂,因而大部分被用来作为化学体修饰电极的修饰材料,详细地研究了它们的电化学性质。实验结果表明,修饰后的电极在酸性水溶液中有非常好的稳定性,上百次的连续扫描和长时间在空气中的放置,对电极的氧化还原性质没有明显的影响。杂化后依然保留了多金属氧酸盐的电化学性质,对过氧化氢、亚硝酸根离子及氯酸根离子的还原有很好的电催化活性。更多还原

【Abstract】 The aim of this thesis is to create a new series of covalently bonded inorganic-organichybrid materials based on polymolybdate clusters by exploiting appropriate metal cations ororganic ligands as linkers according to the concept of crystal engineering. A series ofcompounds have been synthesized and characterized by means of DCC method, aqueoussolution reaction conditions and hydrothermal reaction conditions. The physical and chemicalproperties of these compounds, such as thermal stabilities and redox electrochemicalbehaviors, have also been researched in detail. These compounds are below:（Bu₄N）₂[Mo₆O₁₇（NAr）₂] [Ar = 2,6-（CH₃）₂C₆H₃] （1）（phen）₂[Cu₂（ac）₂（H₂O）₂(CrMo₆H₆O₂₄)]·10H₂O （2）Na₃（Himi）（imi）( NiMo₆H₆O₂₄)·H₂O （2） , （3）Na₂[Cu₃（OH）₄（H₂O）₄][β–Mo₈O₂₆]·13H₂O （4）[Co（H₂O）₅]₄[ Co（H₂O）₄][H₃O]₂[Mo₇O₂₄]₂·18H₂O （5）Na[Cu（imi）₂]₇[As₂W₁₈O₆₂]·5 H₂O （6）[Cu（CH₃-imi）₂]₅[AsW₁₂O₄₂]·2 H₂O （7）[Cu（CH₃-imi）₂]₅[PW₁₂O₄₂]·2 H₂O （8）[Cu（CH₃-imi）₂]₅[H₂W₁₂O₄₂]·2 H₂O （9）[Ag（imi）₂]₅[PW₁₁O₃₉Co（imi）]·3 H₂O （10） Compound 1 was synthesized according to DCC method. The formation of covalentbonds between organic fluorescence molecule and polyoxometalate could efficiently quenchthe fluorescence intensity of organic fluorescence molecule, with a fluorescence quencherefficiency of 87.7%. Compound 2 and 3 were obtained in aqueous solution illustrating 1Dchannels in the structure. Compound 4 and 5, possessing 3D covalently bonded architecture,were also synthesized in aqueous solution. Compound 6-10 were synthesized viaself-assembly under hydrothermal reaction conditions. It is noteworthy that compound 10,taking into account the supramolecular interactions in the structure, has the architecture ofpolypseudo-rotaxane. X-ray diffraction analysis reveals that 10 comprises cationic Ag（imi）2nn-two-dimentional （2D） netlike frameworks parallel to the [0 1 0] direction. To the best of ourknowledge, 10 is the first 1D-in-2D entangled system incorporating polyoxometalates. Thetitle compound 10 has potential application in fluorescencent materials due to the intenseemission at 469nm.All these compounds are highly insoluble in water and common organic solvents due tothe covalently bonded interactions. Therefore, most of these compounds are employed tofabricate the three-dimensional bulk-modified carbon paste electrodes （CPEs） to research ontheir electrochemistry and electrocatalytic properties towards the reduction of chlorate,hydrogen peroxide and nitrite. Compared with those conventional POM-modified electrodes,these hybrid-modified CPEs show good stability owing to their insolubility in aqueoussolution.更多还原