| 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)RuⅣ-O-RuⅣ(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)RuⅣ-O-RuⅣ(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[Mn2ⅡMn14ⅢP8W36O164]26- indicate that some MnⅡof Mn center are oxidized to MnⅢ.The magnetic properties of [{Mn(H2O)Mn2PW9O34}2(PW6O26)]17-,[{Mn(H2O)Mn2PW9O34}2(PW6O26)]16-,[Mn2ⅡMn14ⅢP8W36O164]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.
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