2000 Fiscal Year Final Research Report Summary
Metal Ion Collection Systems Based on the Ligned Basicity Change on Redox Reactions of Some Metal Complexes
| Project/Area Number |
09554037
|
|---|
| Research Category |
Grant-in-Aid for Scientific Research (B).
|
| Allocation Type | Single-year Grants |
|---|
| Section | 展開研究 |
|---|
| Research Field |
Inorganic chemistry
|
|---|
| Research Institution | HOKKAIDO UNIVERSITY |
|---|
Principal Investigator |
SASAKI Yoichi Hokkaido Univ., Grad.School of Sci., Prof., 大学院・理学研究科, 教授 (30004500)
|
|---|
| Co-Investigator(Kenkyū-buntansha) |
KANESATO Masatoshi Tohoku National Industrial Research Institute, Functional Molecules Section, Senior Researcher, 東北工業技術研究所・機能化学部, 主任研究官
SUZUKI Toshishige Tohoku National Industrial Research Institute, Chief Senior Researcher, 東北工業技術研究所, 首席研究官
ABE Masaaki Hokkaido Univ., Grad.school of Sci., Inst., 大学院・理学研究科, 助手 (90260033)
|
|---|
| Project Period (FY) |
1997 – 2000
|
| Keywords | Metal-Metal Bond / Transition Metal Elements / Functional Electrode / Enzyme Model Complexes / Metal Cluster Complexes / Redox Reactions / Electrode Reactions / Catalytic Reactions |
|---|
| Research Abstract |
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.
|
