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

双核配合物的氧化桥碱度随着金属离子氧化态的变化而发生显著变化。因此，通过改变金属的氧化态来控制氧化桥与各种路易斯酸（如金属离子）的相互作用是可能的。本工作旨在制备表面自组装的金属配合物单层电极，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)通过(i)与烷基硫化物混合单层和（ii）含有c - co - nh基团的链之间的氢键，建立了构建Au自组装多核金属配合物单层的方法。(2)定量研究了氧桥接铋配合物在金表面的质子耦合电子转移行为。Diiron alalaog被认为是生物Diiron中心的模型，在溶液中对氧化还原反应不稳定，已经成功地研究了pH范围为1和12的pH电位分布。本文首次对模型Fe-O-Fe配合物的氧化态和还原态的pKa值进行了估计。(3)首次定量研究了质子以外的路易斯酸偶联氧化还原反应。因此，例如，Al^<3+ b>离子在氧化物桥上的相互作用比质子对金属离子氧化态更敏感。(4)通过控制金属氧化态，在Au电极上建立了三核氧中心Ru配合物的逐步寡聚反应。该方法有望在电极表面构建各种超分子组件。

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.