Synthesis of Extended Fullerenyl Cations and Development of Their Functional Monolayers

1)烷基化C_(70)&gt；阳离子的生成与观察区域选择性地合成了富勒烯醇氯_2CH-C_(&t；70)-OH。该富勒烯醇在CF3SO3H中电离，可生成第一个烷基化的C&gt；70&gt；阳离子Cl2CH-C&lt；70&gt；^+。通过对氯离子的S_n1溶解反应速率的研究，估算了电离自由能，结果表明，阳离子Cl_2CH-C_&lt；70&gt；^+的热力学稳定性与相应的阳离子(CH_3-C_&lt；60&gt；60&gt；^+)几乎相同。用CF_3SO_3H处理富勒烯醇CH_3-C_(60)-OH，成功地生成了最简单的烷基化富勒烯基阳离子，并用核磁共振和可见-近红外光谱对其进行了观察。3)烷基化阳离子的分离在中性有机溶剂CH_2Cl2中也能生成。此外，通过在CH_2Cl2溶液中加入CS_2来沉淀盐ClCH_2-C_&lt；60&gt；^+SbCl_6^-，可以分离出固体盐ClCH_2-C_&lt；60+SbCl_6^-。4)用烷基化的C_t；60&gt；阳离子在二氧化硅上形成单层ClCH_2-C_&lt；60&gt；-O-基团可以通过用氯化的CH_2Cl2溶液处理硅片或二氧化硅而形成。椭圆偏振光谱和吸收光谱表明该单分子膜具有较高的表面覆盖率(6 nm^2/molec)。

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.