| Project/Area Number |
11305061
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| Research Category |
Grant-in-Aid for Scientific Research (A)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
工業物理化学
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| Research Institution | Tokyo Metropolitan University |
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Principal Investigator |
IYODA Tomokazu Tokyo Metropolitan University, Graduate School of Engineering, Professor, 工学研究科, 教授 (90168534)
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| Co-Investigator(Kenkyū-buntansha) |
KAWAI Tadashi Tokyo Metropolitan University, Graduate School of Engineering, Professor, 工学研究科, 教授 (00087298)
ASAOKA Sadayuki Tokyo Metropolitan University, Graduate School of Engineering, Research Associate, 工学研究科, 助手 (50336525)
ABE Jiro Tokyo Metropolitan University, Graduate School of Engineering, Associate Professor, 工学研究科, 助教授 (70211703)
松下 未知雄 東京大学, 大学院・総合文化研究科, 助手 (80295477)
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| Project Period (FY) |
1999 – 2001
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| Project Status |
Completed (Fiscal Year 2001)
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| Budget Amount *help |
¥37,240,000 (Direct Cost: ¥36,100,000、Indirect Cost: ¥1,140,000)
Fiscal Year 2001: ¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000)
Fiscal Year 2000: ¥6,600,000 (Direct Cost: ¥6,600,000)
Fiscal Year 1999: ¥25,700,000 (Direct Cost: ¥25,700,000)
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| Keywords | Photoelectrochemical Control / Spin Functional Unit / Conjugated Assembly / Conjugated Polyviologen / Redox-active Ligand / Photo-induced Electron Transfer in Crystal / Log-satcking Structure / Photo-Induced Radical Pair / スピン機能単位 / 全共役ポリビオローゲン / レドックス制御 / 機能性ラジカル / 分子磁性 / 光誘起安定ラジカル対 / ヘキサアリールビスイミダゾール / ローフィルラジカル / 二量化反応 / ラジカル対の分子構造 / 共役組織化 / ビオローゲン / 電子スピン / ビラジカル / 酸化還元電位 / 光制御 / スピン整列 / β-ジケトン |
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| Research Abstract |
Multi-step redox processes are reported in several it-conjugated assemblies of photoelectrochemically active pyridinium units, leading to function-integrated molecular assembly. The strategy has been set to strongly link each redox active unit and then to understand the correlated redox properties, (1) The arylene-linked viologen dimers showed four-step reduction processes in which mono-radical, triplet diradical, half and full quinoid structures are controlled photoelectrochemically. (2) The coordination assembly of bidentate pyridyl pyridinium ligands with paramagnetic metal ions exhibited photochemically tunable spin ordering through antiferromagnetic coupling of the intervening pyridyl radicals. (3) The d-π-dependent multi-step redox processes were demonstrated in various bis(pyridinio)-β-diketone metal complexes, together with their discotic columnar structures. The interaction path analysis giving a guideline for the coming molecular devices with electronic communication will be discussed. Interestingly, triplet ground state was confirmed in inter-ligand trans-configuration and intra-ligand configuration of two pyridinylradicals, while the inter-ligand cis-configuration was thermally excited triplet state, i.e., singlet biradical in the ground state. The electrochemical control of both geometric and electronic structures of the helical conjugated polymers will be also introduced by precisely fabricating pyridinium units in poly (arylisocyanide). Additionally, new modification of conducting polymers will be also introduced by anodic nucleophilic substitution of pyridine derivatives. Remarkable progress has been made in the study of well-designed coordination polymers to take the major place in supramolecular chemistry, which is providing various kinds of nano-structures, in several-to-decades nanometer scales, by self-assembly of small building blocks.
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