| Project/Area Number |
16074211
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| Research Category |
Grant-in-Aid for Scientific Research on Priority Areas
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| Allocation Type | Single-year Grants |
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| Review Section |
Science and Engineering
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| Research Institution | Kyushu University |
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Principal Investigator |
KIMIZUKA Nobuo Kyushu University, Department of Chemistry and Biochemistry, Graduate School of Engineering, Professor (90186304)
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| Co-Investigator(Kenkyū-buntansha) |
MATSUURA Kazunori Department of Chemistry and Biochemistry, Graduate School of Engineering, Assocjate professor (60283389)
MORIKAWA Masa-aki Department of Chemistry and Biochemistry, Graduate School of Engineering, Assistant professor (10363384)
KUROIWA Keita Department of Chemistry and Biochemistry, Graduate School of Engineering, Assistant professor (70336006)
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| Project Period (FY) |
2004 – 2007
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| Project Status |
Completed (Fiscal Year 2007)
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| Budget Amount *help |
¥15,500,000 (Direct Cost: ¥15,500,000)
Fiscal Year 2007: ¥4,000,000 (Direct Cost: ¥4,000,000)
Fiscal Year 2006: ¥4,000,000 (Direct Cost: ¥4,000,000)
Fiscal Year 2005: ¥4,000,000 (Direct Cost: ¥4,000,000)
Fiscal Year 2004: ¥3,500,000 (Direct Cost: ¥3,500,000)
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| Keywords | Self-assembly / one-dimensional metal complex / spin crossover / adaptive molecular cleft / azobenzene / bydrogen bond / スピン転移 / ゲル / 液晶 / フィルム / 蛍光 / エネルギー移動 / ナノ金属錯体 / ナノワイヤ / トリアゾール / 発色団 / 酸化還元 / オルガノゲル / 一次元錯体 / 分子認識 / 超分子 / サーマルヒステリシス |
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| Research Abstract |
Lipophilic modification of one-dimensional metal complexes provide self-assembly of molecular wires which exhibit unique solution properties not accessible from conventional inorganic, polymer or supramolecular chemistry. In this study, we focused on the creation of molecular binding clefts on the surface of lipophilic linear metal complexes.
Supramolecular Fe(II) complexes bridged by dodecyloxypropyl-1, 2, 4-triazole was newly developed. It exhibited sluggish spin crossover behavior in the solid state. Co-casting of equimolar dodecanol or tetradecanol with the Fe(II)triazole complex afforded composite films in which alcohol molecules were bound to the complex via van der Waals interactions and ionic hydrogen bonding. Interestingly, thermal hysteresis was induced in the spin crossover characteristics of ternary cast films. By doping alcohol molecules, lamellar structures at lower temperatures (LS state) were converted to hexagonal structures at higher temperatures (HS state), and such s
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tructural transformation of basic structures caused generation of bistability. This study provides a first example of supramolecular control on the thermal spin crossover phenomena. This concept was further applied to the combination of Fe(II) triazole complexes and liquid crystals, which demonstrated the formation of spin crossover liquid crystalline gels.
To photoregulate the morphology of 1D Fe(triazole)3 complexes, azobenzene chromophores were introduced. UV light irradiation of the azobenzene-containing Fe(II) triazole complex in a yellow chlorocyclohexane gel caused fluidization into an orange-colored solution. In AFM, parallel-aligned rod-like structures in nanosheets were observed for the gel samples. UV irradiation causes structural transformation to undulating molecular wire structures. 4 Finally, electrochemical control on organogels was investigated. Cyclic voltammetry indicates that linear Fe(II) triazole complex display reversible oxidation and reduction in chloroform. Their gel-to-sol transition characteristics are controllable based on oxidation/reduction of iron ions. Thus, stimuli-responsive molecular wires of coordination chains were created, which showed unique physical properties. Less
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