| Project/Area Number |
13450352
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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 |
工業物理化学
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| Research Institution | Kyoto University |
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Principal Investigator |
TANAKA Kazuyoshi Kyoto University, Molecular Engineering, Professor, 工学研究科, 教授 (90155119)
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| Co-Investigator(Kenkyū-buntansha) |
ITO Akihiro Kyoto University, Molecular Engineering, Research associate, 工学研究科, 助手 (90293901)
HIROYUKI Fueno Kyoto University, Molecular Engineering, Research associate, 工学研究科, 助手 (30212179)
MISAKI Yohji Kyoto University, Molecular Engineering, Associate professor, 工学研究科, 助教授 (90202340)
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| Project Period (FY) |
2001 – 2003
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| Project Status |
Completed (Fiscal Year 2003)
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| Budget Amount *help |
¥13,300,000 (Direct Cost: ¥13,300,000)
Fiscal Year 2003: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 2002: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 2001: ¥10,500,000 (Direct Cost: ¥10,500,000)
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| Keywords | Organic molecular metal / Quantum functional material / Photo conductivity / Photo induced ferromagnetism / Electronic structure / Photo induced electron-transfer / 光導電性 / 分子内光電子移動 / サイクリックボルタンメトリー / 電気伝導度 |
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| Research Abstract |
(1) Hybrid system composed of TTF fused with 1,3-dithiol-2-ylidene (DT TTF) and C60 (1) has been designed, and its electronic structure has been investigated. The molecular orbital calculation of the unsubstituted-1 suggests that the DT TTF and C_<60> units mainly contribute to the HOMO and LUMO, respectively. The DT TTF and C_<60> moieties have positive and negative, respectively, indicating intramolecular charge-transfer. On the other hand, HOMO-LUMO gap of 1 is significantly smaller by 3.02 and 1.07 eV compared with those of DT TTF and C_<60>, respectively.
(2) Several derivatives of 1 have been synthesized. Cyclic voltammogram of 1 consists of two reversible oxidation waves corresponding to the TTF and four reduction ones due to C_<60> moiety. The oxidation potentials are higher than those of the corresponding DT TTF derivative due to electron-withdrawing effect of C_<60>. In a similar manner, the reduction potentials are more negative than those of C_<60> because of electron-donating effect of the donor moiety. They showed electrical conductivity of σ_<rt> = 10^<-8>S cm^<-1> on compressed pellets.
(3) Several derivatives of oligo-fused extended-TTF, in which thiophene is inserted, have been synthesized. Cyclic voltammogram of the tris-fused derivative consists of two pairs of two-electron transfer waves and two pairs of one-electron ones, while the bis-fused analog exhibits four pairs of one-electron transfer waves. The above results indicate that the positive charges delocalize on the whole molecule. In the UV vis spectra of these oligo-fused extended-TTFs, the absorption maxima appeared around 485 nm, and no significant shift to the longer wavelength region was observed derived from increase of extended-TTF units.
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