Synthesis of Extended Fullerenyl Cations and Development of Their Functional Monolayers
| Project/Area Number |
16550035
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | KYOTO UNIVERSITY |
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Principal Investigator |
KITAGAWA Toshikazu Kyoto University, Institute for Chemical Research, Assoc. Professor, 化学研究所, 助教授 (20183791)
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| Co-Investigator(Kenkyū-buntansha) |
KOMATSU Koichi Kyoto University, Institute for Chemical Research, Professor, 化学研究所, 教授 (70026243)
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| Project Period (FY) |
2004 – 2005
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| Project Status |
Completed (Fiscal Year 2005)
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| Budget Amount *help |
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2005: ¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 2004: ¥2,100,000 (Direct Cost: ¥2,100,000)
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| Keywords | Fullerene / Carbocation / Fullerenol / NMR / Thermodynamic Stability / Monolayer / カルボカチオン塩 / シリカ / 活性化自由エネルギー |
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| Research Abstract |
1) Generation and Observation of a Alkylated C_<70> Cation
Fullerenol Cl_2CH-C_<70>-OH was synthesized regioselectively. The first alkylated C_<70> cation, Cl_2CH-C_<70>^+ could be generated by the ionization of this fullerenol in CF_3SO_3H. The free energy of ionization, evaluated by the rate study of the S_N1 solvolysis of chloride Cl_2CH-C_<70>-Cl, revealed that cation Cl_2CH-C_<70>^+ has a thermodynamic stability that is almost equal to that of the corresponding C_<60> cation Cl_2CH-C_<60>^+.
2) Generation and Observation of Methylated C_<60> Cation
The methylated C_<60> cation (CH_3-C_<60>^+), most simple alkylated fullerenyl cation, was successfully generated by treating fullerenol CH_3-C_<60>-OH with CF_3SO_3H, and was observed by NMR and vis-NIR spectroscopy.
3) Isolation of Alkylated a C_<60> Cation
Alkylated C_<60> cations could be also generated in CH_2Cl_2, a neutral organic solvent. Furthermore, a salt, ClCH_2-C_<60>^+ SbCl_6^-, could be isolated as solid by precipitating this salt by the addition of CS_2 to the CH_2Cl_2 solution.
4) Formation of a Monolayer on Silica using Alkylated C_<60> Cation
Monolayer of ClCH_2-C_<60>-O- group could be formed by treating the surface of a silicone wafer or silica with a CH_2Cl_2 solution of chloride ClCH_2-C_<60>-Cl. The high surface coverage of this monolayer (6 nm^2/molec) was demonstrated by ellipsometry and absorption spectrometry.
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Report
(3 results)
Research Products
(14 results)
