Construction of fullerene-coated nano-structures using alkylfullerenyl cations

使用烷基富勒烯基阳离子构建富勒烯涂层纳米结构

• 批准号: 14550807
• 负责人: KITAGAWA Toshikazu
• 金额: $ 2.62万
• 依托单位: Kyoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14550807/
• 关键词: fullereneC60; carbocation; solvolysis; pKR+; electron transfer; silica; monolayer; surface coating; カルボカチオン塩; 超強酸; シリコンウエファー; フラーレン; カルボカオチン; pK_R^+

1.Quantitative Determination of the Thermodynamic Stabilities of Alkylfullerenyl CationsThe thermodynamic stabilities of alkylfullerenyl cations were evaluated by the kinetic measurements for the S_N1 solvolysis of chlorides R-C_<60>-Cl and by precise determination of the equilibrium constants of the ionization of fullerenols R-C_<60>-OH. The results of these experiments demonstrated that alkylfullerenyl cations have stabilities comparable to that of the tert-butyl cation.2.Preparation of Alkylfullerenyl Cation as Long-lived Species in Solution and Its Isolation as a SaltThe isolation of C_<60> cations have been considered extremely difficult, owing to the electronegative nature of the C_<60> cage. In the present study, however, treatment of chlorides R-C_<60>-Cl with silver ion (AgSbF_6) or with a Lewis acid (SbCl_5) resulted in successful preparation of RC_<60>^+ the form of a stable solution in neutral organic solvent or in the form of a salt RC_<60>^+ SbCl_5^-. Formerly, these cations could be prepared only as solutions in strongly acidic solvents.3.Coating of Silica Surface with Fullerene Monolayer using Alkylflullerenyl CationA monolayer of fullerene could be prepared on the surface of silicon wafer, by dipping the wafer in a solution of R-C_<60>-Cl. This can be interpreted as a result of the reaction of an intermediate cation RC_<60>^+ with hydroxyl groups on the surface of the oxide layer. This observation demonstrated that the high reactivity of RC_<60>^+ would be useful for the formation of a C_<60> monolayer on solid surfaces covered with hydroxyl groups.

1.烷基富勒烯基阳离子热力学稳定性的定量测定通过对氯化物R-C_<60>-Cl的S_N1溶解动力学测量和对富勒烯醇R-C_<60>-OH电离平衡常数的精确测定，评价了烷基富勒烯基阳离子的热力学稳定性。实验结果表明，烷基富勒烯基阳离子具有与叔丁基阳离子相当的稳定性。烷基富勒烯基阳离子在溶液中的长寿命的制备及其作为盐的分离由于C_<60>笼的电负性，分离C_<60>阳离子一直被认为是极其困难的。然而，在本研究中，用银离子（AgSbF_6）或路易斯酸（SbCl_5）处理氯化物R-C_<60 bbb_0 - cl，成功地制备了RC_<60 bbb_1 ^+，在中性有机溶剂中以稳定溶液的形式或以盐RC_<60 bbb_2 ^+ SbCl_5^-的形式。以前，这些阳离子只能作为溶液在强酸性溶剂中制备。将硅片浸在R-C_<60>-Cl溶液中，可以在硅片表面制备单层富勒烯涂层。这可以解释为中间阳离子RC_<60>^+与氧化层表面的羟基反应的结果。这一观察结果表明，RC_<60>^+的高反应性将有助于在羟基覆盖的固体表面上形成C_<60>单层。

项目成果

Toshikazu Kitagawa: "Synthesis and Properties of Ionic Hydrocarbons Containing an Alkylated Fullerene Ion"J.Synth.Org.Chem.Jpn.. 61. 797-805 (2003)

Toshikazu Kitakawa：“含有烷基化富勒烯离子的离子烃的合成和性质”J.Synth.Org.Chem.Jpn.. 61. 797-805 (2003)

峯岸信也, 鎌田 潤, 竹内賢一, 小松紘一, 北川敏一: "Acid-Catalyzed Conversion of 7-Ethynyl- and 7-Vinyl-cycloheptatrienes to Substituted Benzene Derivatives"European Journal of Organic Chemistry. 18号. 3497-3504 (2003)

Shinya Minegishi、Jun Kamata、Kenichi Takeuchi、Koichi Komatsu、Toshikazu Kitakawa：“7-乙炔基-和 7-乙烯基-环庚三烯到取代苯衍生物的酸催化转化”欧洲有机化学杂志 18. 3497-3504 (2003)。

Toshikazu Kitagawa, Yangsoo Lee, Koichi Komatsu: "Electron-Transfer Induced Substitution of Alkylated C_<60> Chlorides with Proton Sponge"J.Org.Chem.. 69. 263-269 (2004)

Toshikazu Kitakawa、Yangsoo Lee、Koichi Komatsu：“用质子海绵进行烷基化 C_<60> 氯化物的电子转移诱导取代”J.Org.Chem.. 69. 263-269 (2004)

李 洋洙, 北川敏一, 小松紘一: "Electron-Transfer Induced Substitution of Alkylated C_<60> Chlorides with Proton Sponge"The Journal of Organic Chemistry. 69巻2号. 263-269 (2004)

Yosoo Lee、Toshikazu Kitakawa、Koichi Komatsu：“烷基化 C_<60> 氯化物与质子海绵的电子转移诱导取代”有机化学杂志，第 69 卷，第 2. 263-269 期（2004 年）。

北川敏一, 李 洋洙, 花村政暁, 坂本晴美, 紺野博文, 竹内賢一, 小松紘一: "Nucleophilic Substitution of Alkylchlorodihydro [60] fullerenes : Thermodynamic Stabilities of Alkylated C_<60> Cation Intermediates"Chemical Communications. 3062-3063 (2002)

Toshikazu Kitakawa、Yosu Lee、Masaaki Hanamura、Harumi Sakamoto、Hirofumi Konno、Kenichi Takeuchi、Koichi Komatsu：“烷基氯二氢[60]富勒烯的亲核取代：烷基化 C_<60> 阳离子中间体的热力学稳定性”化学通讯 3062-3063（2002 年）。 ）