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Development of the Organic Method for the Synthesis of Endohedral Fullerenes

内嵌富勒烯有机合成方法的进展

基本信息

批准号：
16350021
负责人：
KOMATSU Koichi
金额：
$ 9.28万
依托单位：
Kyoto University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
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

项目摘要

(1)The first endohedral fullerene encapsulating molecular hydrogen, H2@C60, was synthesized by so-called "molecular surgical approach". Thus, an 8-membered-ring orifice was formed on the surface of fullerene C60, via cycloaddition of a 1,2,4-triazine derivative to C60, followed by its enlargement into a 12-membered ring by oxidation with singlet oxygen. The opening was further enlarged into a 13-membered ring by insertion of sulfur into the rim of the orifice, and then high-pressure hydrogen was applied to afford an open-cage fullerene encapsulating H2 in 100%. The molecular hydrogen inside the cage was directly observed by means of MEM X-ray analysis using synchrotron radiation. Then the orifice was closed, while retaining the encapsulated hydrogen, by a four-step synthesis to afford H2@C60 in about 9% overall yield from the starting C60.(2)The similar treatment of C70 afforded H2@C70 and also a small amount, of (H2)2@C70. The motion of the two hydrogen molecules in the open-cage [70]fullerene was observed by variable temperature 1H NMR measurement.(3)The electronic interaction between the encapsulated hydrogen and the outer pi-system of fullerene cage was shown to be rather small by electronic measurement and also by 13C NMR spectroscopy.(4)Hydrogen isotopes, i.e., H2, HD, and D2, were also encapsulated into the derivatives of open-cage fullerene. D2@C60 was synthesized and the difference between H2@C60 was clarified.5) Helium was found to be encapsulated into the open-cage fullerene much more readily than hydrogen. [4] The closed-cage fullerene He@C60 was synthesized in the same way as that for H2@C60.

（1）采用分子外科方法合成了第一个包封分子氢的富勒烯H_2@C_60。因此，一个8元环孔形成在富勒烯C60的表面上，通过环加成的1，2，4-三嗪衍生物到C60，然后通过氧化与单线态氧，其扩大成一个12元环。通过在孔的边缘插入硫，将开口进一步扩大成13元环，然后施加高压氢气，以提供100%包封H2的开笼富勒烯。通过使用同步辐射的MEM X射线分析直接观察笼内的分子氢。然后关闭孔，同时保留包封的氢，通过四步合成以从起始C60以约9%的总产率提供H2@C60。（2）C_（70）的类似处理得到H_2@C_（70）和少量的（H_2）_2@C_（70）。通过变温~ 1H NMR测量观察到了两个氢分子在开笼[70]富勒烯中的运动。（3）电子测量和~（13）CNMR谱表明，包封氢与富勒烯笼外π体系之间的电子相互作用很小。（4）氢同位素，即，H2、HD和D2也被封装到开笼富勒烯衍生物中。合成了D2@C60，并澄清了H2@C60之间的差异。5）发现氦比氢更容易封装到开笼富勒烯中。[4]以与H2@C60相同的方式合成了闭笼富勒烯He@C60。

项目成果

期刊论文数量（28）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Floating Single Hydrogen Molecule in an Open-Cage Fullerene.

开笼富勒烯中漂浮的单个氢分子。

DOI：
发表时间：
2005
期刊：
Angew.Chem.Int.Ed. 44
影响因子：
0
作者：
Y.Matsuo;H.Isobe;T.Tanaka;Y.Murata;M.Murata;K.Komatsu;E.Nakamura;Y.Ie;K.Komatsu;S.Inoue;C.M.Stanisky;N.Hatanaka;N.Negishi;H.Sawa
通讯作者：
H.Sawa

水素利用技術集成、Vol..2

氢气利用技术集，第.2卷