Synthesis and structure of an open-cage thiafullerene C69S: reactivity differences of an open-cage C70 tetraketone relative to its C60 analogue.
Synthesis and structure of an open-cage thiafullerene C69S: reactivity differences of an open-cage C70 tetraketone relative to its C60 analogue.
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DOI：
10.1021/ja504054s
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发表时间：
2014-06
影响因子：
15
通讯作者：
Rui Zhang;Tsukasa Futagoishi;M. Murata;A. Wakamiya;Y. Murata
中科院分区：
文献类型：
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作者：
Rui Zhang;Tsukasa Futagoishi;M. Murata;A. Wakamiya;Y. Murata
以开笼型C70二酮与亲核氧化剂反应，合成了具有13元开环和双（半缩醛）部分的开笼型C70富勒烯。笼口的大小可以通过随后的脱水反应而扩大。由此得到的开笼C70四酮在四（二甲胺）乙烯存在下与单质硫反应，形成了具有12元开环的开笼C69S硫富勒烯的第一个例子。这种含硫杂富勒烯的形成反映了开笼C70四酮相对于其C60类似物的显著不同的化学反应性。通过单晶x射线衍射分析确定了所有新化合物的结构，并检查了噻吩烯C69S的电化学性能，并与相应的C70类似物进行了比较。
An open-cage C70 fullerene with a 13-membered ring-opening and a bis(hemiacetal) moiety was synthesized by the reaction of the corresponding open-cage C70 diketone with nucleophilic oxidizing agents. The size of the cage opening could be expanded by a subsequent dehydration reaction. Reaction of the thus obtained open-cage C70 tetraketone with elemental sulfur in the presence of tetrakis(dimethylamino)ethylene resulted in the formation of the first example of an open-cage C69S thiafullerene with a 12-membered ring-opening. The formation of this sulfur-containing heterofullerene reflects a significantly different chemical reactivity for the open-cage C70 tetraketone relative to its C60 analogue. The structures of all novel compounds were unambiguously determined by single crystal X-ray diffraction analyses, in addition to which the electrochemical properties of the thiafullerene C69S were examined and compared with those of the corresponding C70 analogue.