| Project/Area Number |
11440199
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| Research Category |
Grant-in-Aid for Scientific Research (B).
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Inorganic chemistry
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| Research Institution | Osaka City University |
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Principal Investigator |
TADOKORO Makoto OSAKA CITY UNIVERSITY, GRADUATE SCHOOL OF SCIENCE, ASSOCIATE PROFESSOR, 理学部, 助教授 (60249951)
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| Project Period (FY) |
1999 – 2000
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| Project Status |
Completed (Fiscal Year 2000)
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| Budget Amount *help |
¥10,700,000 (Direct Cost: ¥10,700,000)
Fiscal Year 2000: ¥1,900,000 (Direct Cost: ¥1,900,000)
Fiscal Year 1999: ¥8,800,000 (Direct Cost: ¥8,800,000)
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| Keywords | HYDROGEN BOND / Re COMPLEX / MIXED VALANCE STATE / BIIMIDAZOLE / TAUTOMERIZATION / HYDROGEN BONDED DIMMER / SUPRAMOLECULE / CRYSTALENGINEERING / ゼオライト / 酸化還元 / 分子性結晶 |
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| Research Abstract |
Realization on a proton and an electron cooperative system using redox process of transition metal ions has required making up of a new molecular system with a mixed valence complex through a strong hydrogen-bonding interaction. We have already demonstrated that molecular building systems with a metal ion and 2, 2-bimidazolate monoanion (Hbim^<-1>) can be formed not only the ordered super-structures by self-organization using complementary NH-N hydrogen bonds between the ligands. But also variation on oxidation number of a metal ion can greatly change the pKa_1 and the pKa_2 values of two NH protons in the ligand. Here it is presented that a new molecular system, [Re^<III>Cl^2(PPh_3)(Hbim)]_2 complex (1), with a hydrogen-bonded dimmer formation was prepared. Interestingly, the cyclic voltammogram on the complex 1 indicated reversible and quasi-reversible redox potentials on Re^<II>Re^<II>【tautomer】Re^<II>Re^<III>【tautomer】 Re^<III>Re^<III>【tautomer】Re^<III>Re^<IV>【tautomer】Re^<IV>Re^<IV>. Complex 1 will show the bi-functionalities on relation to an electron transfer in the mixed valence state of two Re ions and a proton transfer for tautomerization of complementary intermolecular hydrogen-bonding between two Hbim^<-1> ligands, by measuring on dielectric constant.
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