【作者】 陈愫文；

【导师】 刘伟生；

【作者基本信息】 兰州大学 ， 无机化学， 2008， 博士

【摘要】 本文研究了两个类型的多核配合物,分别为过渡金属取代的多金属氧酸盐及以邻菲啰啉为骨架的酰胺型稀土多核配合物。论文的第一部分包括:一、简要介绍了饱和型和缺位型Keggin和Dawson杂多阴离子的结构;综述了贵金属取代的缺位型多金属氧酸盐和过渡金属多取代的缺位型多金属氧酸盐。二、通过水热反应的方法得到含有高价Ru的多阴离子[{PW₁₁O₃₉}₂{（HO）Ru^Ⅳ-O-Ru^Ⅳ（HO）}]^10-。对此多阴离子在固体状态和液体状态下分别做了X-射线晶体衍射,XAFS,Raman,IR,SQUID,（31）^p NMR,（183）^W NMR,紫外光谱及电化学研究。所得数据都表明,多阴离子的结构为{（HO）Ru^Ⅳ-O-Ru^Ⅳ（HO）}单元连接了两个[α-PW₁₁O₃₉]^7-。三、以直接组装为思路通过控制反应条件得到了五个像胶囊一样填入Keggin或α-[P₈W₄₈O₁₈₄]^40-中的Mn簇,并对其进行了结构表征。对多阴离子[{Mn（H₂O）Mn₂PW₉O₃₄}₂(PW₆O₂₆)]^n-（n=16,17）及[Mn^Ⅱ₂Mn^Ⅲ₁₄P₈W₃₆O₁₆₄]^26-进行了紫外光谱及电化学研究,证明了其结构中含有Mn^Ⅲ,并通过研究磁性能得知[{Mn（H₂O）Mn₂PW₉O₃₄}₂(PW₆O₂₆)]^17-、[{Mn（H₂O）Mn₂PW₉O₃₄}₂(PW₆O₂₆)]^16-、[Mn^Ⅱ₂MnⅢ₁₄P₈W₃₆O₁₆₄]^26-及[Mn₈P₈W₄₈O₁₈₄]^24-都具有反铁磁性。第二部分中阐述了:四、主要介绍DNA的结构、金属配合物与DNA之间的相互作用以及多核化合物的生物活性方面的研究。五、利用荧光法、紫外光谱法、粘度法和凝胶电泳实验研究了以邻菲啰啉为骨架的多核稀土配合物与小牛胸腺DNA之间的相互作用方式,实验结果表明:它们与DNA之间均存在着插入结合方式;在近生理条件下均可切割pBR322 DNA。由于配体末端基的不同从而决定了配合物与DNA结合的行为。更多还原

【Abstract】 This thesis studies two kinds of polynuclear complexes,which concern the transition metal substituted polyoxometalates and the lanthanide polynuclear complexes of amide-base 1,10-phenanthroline derivatives.The first part can be divided into the following three aspects:1.The structure of Keggin and Dawson polyoxometalates has been concisely introduced.The research progress for the noble-metal derivative of polyoxometalates and the transition metal substituted multivacant polyoxometalates are reviewed.2.The high-valent ruthenium-containing[{PW₁₁O₃₉}₂{（HO）Ru^Ⅳ-O-Ru^Ⅳ（HO）}]^10- anion has been synthesized by hydrothermal reaction.It is characterized in the solid-state and in solution by X-ray diffraction,XAFS,Raman,IR,SQUID,UV-visible, multinuclear(³¹p and ¹⁸³W) NMR spectroscope and electrochemistry.All results indicate that the polyanion contains an {（HO）Ru^Ⅳ-O-Ru^Ⅳ（HO）} moiety that links two monovacant[α-PW₁₁O₃₉]^7- subunits.3.Synthetical method of the directed-assembly and the structural and magnetic characterization of five manganese clusters encapsulated in Keggin orα-[P₈W₄₈O₁₈₄]^40- fragments are presented.The five ployanions show how it is possible to increase the nuclearity of the clusters（from 1 and 6 to 16） by slightly changing the "environment". The results of the UV-visible spectroscopy and electrochemistry of [{Mn（H₂O）Mn₂PW₉O₃₄}₂(PW₆O₂₆)]^n-（n=16,17） and[Mn₂^ⅡMn₁₄^ⅢP₈W₃₆O₁₆₄]^26- indicate that some Mn^Ⅱof Mn center are oxidized to Mn^Ⅲ.The magnetic properties of [{Mn（H₂O）Mn₂PW₉O₃₄}₂(PW₆O₂₆)]^17-、[{Mn（H₂O）Mn₂PW₉O₃₄}₂(PW₆O₂₆)]^16-、[Mn₂^ⅡMn₁₄^ⅢP₈W₃₆O₁₆₄]^26-and[Mn₈P₈W₄₈O₁₈₄]^24- are antiferromagnetic.The main contents of the second part are divided into two aspects:4.DNA structures,interactions of metal complexes with DNA and antitumor activities of polynuclear complexes are described.5.The spectroscopic methods and viscosity measurements are used to investigate the interaction between the calf thymus DNA（CT-DNA） and lanthanide complexes of amide-based 1,10-phenanthroline derivatives.The results indicate that both complexes bound to DNA via an intercalative mode.Furthermore,at physiological pH and temperature,the two complexes are also found to promote the cleavage of plasmid pBR322 DNA.The terminal group of the 1,10-phenanthroline derivatives is the main factor that determines the DNA binding behavior of the two complexes.更多还原