Synthesis of Extended Fullerenyl Cations and Development of Their Functional Monolayers

扩展富勒烯基阳离子的合成及其功能单分子层的开发

• 批准号: 16550035
• 负责人: KITAGAWA Toshikazu
• 金额: $ 2.3万
• 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: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16550035/
• 关键词: 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

1) Generation and Observation of a Alkylated C_<70> CationFullerenol 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> CationThe 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> CationAlkylated 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> CationMonolayer 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.

1)区域选择性合成C_<70>-OH烷基化C_<70>-OH的生成与观察。富勒烯醇在CF_3SO_3H中电离生成了第一个烷基化C_<70>^+阳离子Cl_2CH-C_<70>^+。通过对氯离子Cl_2CH-C_<70>-Cl的S_N1溶解速率的研究，得到了Cl_2CH-C_<70>^+的热力学稳定性，与相应的C_<60>阳离子Cl_2CH-C_<60>^+的热力学稳定性基本相当。2)甲基化C_<60>阳离子的生成与观察用CF_3SO_3H处理富勒烯醇CH_3-C_<60>-OH，成功生成了最简单的烷基化富勒烯基阳离子C_<60>阳离子（CH_3-C_<60>^+）。并通过核磁共振和可见-近红外光谱进行了观察。3)烷基化C_<60>阳离子的分离在中性有机溶剂CH_2Cl_2中也可生成烷基化C_<60>阳离子。此外，通过在CH_2Cl_2溶液中加入CS_2，可以分离出ClCH_2-C_<60>^+ SbCl_6^-盐。4)烷基化C_<60>阳离子在二氧化硅表面形成ClCH_2-C_<60>- o -基团单层用ClCH_2-C_<60>- cl的CH_2Cl_2溶液处理硅片或二氧化硅表面，可形成ClCH_2-C_<60>- o -基团单层。椭偏仪和吸收光谱分析表明，该单层膜具有较高的表面覆盖率（6 nm^2/分子）。

项目成果

Generation and Properties of a Novel Alkylated C_<70> Cation

新型烷基化C_<70>阳离子的生成及其性质

• 发表时间: 2005
• 期刊: Angew. Chem. Int. Ed. 44
• 作者: Nakamichi;N.;Kita;M.;Ito;S.;Yamashino;T.;Mizuno;T.;T.Shima;N.Yoshimoto;栗原達夫;T.Nakamura;M.Kinoshita;Masanori Ono;Y.yamashita;A.Yamada;Masahiro Kawao;Wei Huang;A.Morita;K.Yakushiji;K.Ishii;Y.Utsmi;H.Matsueda;T.Yamashita;S.E.Bames;T.Tohyama;K.Ishii;Y.Asai;福山秀敏;M.Matsukawa;K.Kudo;K.Shibata;M.Terauchi;Y.Taguchi;Y.Rikishi;H.Toh;M.Shiraishi;T.Higuchi;S.Imada;I.Kezsmarki;M.Matsubara;H.Nojiro;Y.doi;M.Kosaka;K.Ohwada;S.Ishihara;D.Okuyama;D.Okuyama;K.Iwasa;K.Kuzushita;M.Sakata;K.Kuwahara;D Okuyama;M.Tsubota;K.Ishii;K.Kaji;N.Takahashi;T.Kanaya;K.Nakanura;K.Yoshimune;K.Yoshimune;K.Yoshimune;H.Yamamoto;H.Muramatsu;H.Muramatsu;H.Mihara;A.Kurata;M.Goto;S.Ishida;C.M.Stanisky;K.Komatsu;Y.Miyata;T.Kitagawa
• 通讯作者: T.Kitagawa

MALD1-Fourier Transform Mass Spectrometric and Theoretical Studies of Donor-Acceptor and Donor-Bridge-Acceptor Fullerenes

供体-受体和供体-桥-受体富勒烯的MALD1-傅里叶变换质谱和理论研究

• 发表时间: 2005
• 期刊: Phys.Chem.Chem.Phys. 7
• 作者: 田辺順;川田勇三 他6名;Toshikazu Kitagawa;北川 敏一;Vladimir E.Frankevich;堀江 留美子;小川 紘平;Toshikazu Kitagawa;Vladimir E.Frankevich
• 通讯作者: Vladimir E.Frankevich

Study of Photoinduced Electron Transfer between [60]Fullerene and Proton-Sponge by Laser Flash Photolysis : Addition Effects of Organic Acid

激光闪光光解研究[60]富勒烯与质子海绵之间的光致电子转移：有机酸的添加效应

• 发表时间: 2005
• 期刊: Journal of Physical Chemistry A 109巻28号
• 作者: 田辺順;川田勇三 他6名;Toshikazu Kitagawa;北川 敏一;Vladimir E.Frankevich;堀江 留美子
• 通讯作者: 堀江 留美子

Synthesis and Structure of a New Tetrakis(pentafluorophenyl)borate Salt of the Silver(I) Cation with Novel Trigonal Planar Tris(benzene) Coordination

具有新型三角平面三(苯)配位的新型银(I)阳离子四(五氟苯基)硼酸盐的合成和结构

• 发表时间: 2005
• 期刊: Organometallics 24
• 作者: 田辺順;川田勇三 他6名;Toshikazu Kitagawa;北川 敏一;Vladimir E.Frankevich;堀江 留美子;小川 紘平;Toshikazu Kitagawa;Vladimir E.Frankevich;Rumiko Horie;Kohei Ogawa
• 通讯作者: Kohei Ogawa

Carbon-Rich Compounds: From Molecules to Materials

• DOI: 10.1002/3527607994
• 发表时间: 2006-06
• 作者: M. Haley;R. Tykwinski