Metal Ion Collection Systems Based on the Ligned Basicity Change on Redox Reactions of Some Metal Complexes

双核配合物氧化桥的碱性随金属离子氧化态的变化而显著变化。因此，可以通过改变金属氧化态来控制氧化物桥与各种刘易斯酸如金属离子的相互作用。本工作旨在制备具有这种金属配合物的表面自组装单分子膜的电极，并将其用作可逆的金属离子粘合剂，并建立逐步构建金属配合物低聚物的方法。结果总结如下。（1）建立了利用含烷基硫醚的混合单分子膜和含C-CO-NH-基团的链间氢键作用构筑多核金属配合物Au自组装单分子膜的方法。（2）定量研究了氧桥联钌配合物在金表面的质子耦合电子转移行为。二铁alnalaogs被认为是生物二铁中心的模型，在溶液中对氧化还原反应是不稳定的，已经成功地研究了在pH值为1和12的范围内的pH-电位分布。氧化和还原形式的pKa值已估计为第一次为模型Fe-O-Fe络合物。（3）首次定量研究了质子以外的刘易斯酸与氧化还原反应的耦合。因此，例如，Al ^<3 +>离子在氧化物桥上的相互作用对金属离子的氧化态比质子更敏感。（4）通过控制金属的氧化态，建立了三核钌氧代配合物在Au电极上的逐步低聚反应。该方法有望在电极表面构建各种超分子组装体。

Basicity of oxide bridge of dinuclear complexes changes remarkably with the change in the oxidation states of the metal ions. It is thus possible to control the interaction of the oxide bridge with various Lewis acids like metal ions by changing the metal oxidation states. This work aimed at preparing the electrodes with surface self-assembled monolayers of such metal complexes, and use them as reversible metal-ion binder and to establish the method for the step-wise construction of metal-complex oligomers. The results are summarized as follows.(1)Methods to construct Au self-assembled monolayers of polynuclear metal complexes have been established by using(i)mixed monolayers with alkyl sulfide and(ii)hydrogen bonding between the chains which contain C-CO-NH-groups.(2)Protoncoupled electron transfer behavior of the oxo-bridged biruthenium complexes on gold surface have been quantitatively investigated. Diiron alnalaogs which are considered as models of biological diiron centers and are unstable towards redox reactions in solution, have been successfully studied in terms of pH-potential profiles over pH range of 1 and 12. The pKa values of the oxidized and reduced forms have been estimated for the first time for the model Fe-O-Fe complexes.(3)Coupled redox reactions have been studied quantitatively with Lewis acids other than proton for the first time. Thus, for example, interaction of Al^<3+> ions at the oxide bridge is more sensitive to the metal ion oxidation states than protons.(4)Step-wise oligomerization of the trinuclear oxo-centered Ru complexes on Au electrode has been established by controlling the metal oxidation state. The method is promising in contructing various supramolecular assemblies on electrode surfaces.