Heterofullerenes: Doped Buckyballs
Heterofullerenes: Doped Buckyballs
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DOI：
10.1002/9783527648160.ch9
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发表时间：
2016-12
影响因子：
0.9
通讯作者：
M. Delius;A. Hirsch
中科院分区：
文献类型：
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作者：
M. Delius;A. Hirsch
杂富勒烯是一种具有踢力的巴基球，其中球形骨架中的一个或多个碳原子被杂原子（最常见的是：N、B、Si、O）取代。迄今为止，只有氮杂富勒烯可以通过批量化学合成获得，而其他杂富勒烯已通过激光汽化或电弧放电制备，并且许多竞争者仅在计算机上进行了研究。最简单的氮杂富勒烯 C59N 是单体形式的自由基，这一特性对化学反应性具有重要意义。因此，单加合物C59NR可以通过(C59N)自由基制备，或者通过其氧化形式，即氮杂富勒鎓离子C59N+制备。近年来，人们进行了多次合成尝试来合成难以捉摸的闭壳二氮杂富勒烯 C58N2；在三种情况下，通过 FAB 或 MALDI 质谱实现了该实体的形成和检测。氮杂富勒烯五加合物C59N(R)5的合成是最近的另一项成就，此类化合物的化学性质目前正在研究中。最后，最近关于内嵌金属氮杂富勒烯、氮杂富勒烯碳纳米管豆荚的报道以及C59N作为氢燃料电池优异阴极催化剂的理论研究都表明，该领域的进一步研究可能带来意想不到的好处。
Heterofullerenes are buckyballs with a kick, in which one or several carbon atoms in the spherical framework are replaced by a heteroatom (most commonly: N, B, Si, O). To date, only the azafullerenes are accessible via bulk chemical synthesis, while other heterofullerenes have been prepared by laser vaporization or arc discharge and many contenders have been studied onlyin silico. The simplest azafullerene C59N is a radical in its monomeric form, a property that has significant implications for the chemical reactivity. Monoadducts C59NR can thus be prepared via the (C59N) radical, or alternatively via its oxidized form, namely, the azafulleronium ion C59N+. In recent years, several synthetic attempts for the synthesis of the elusive closed‐shell diazafullerene C58N2were undertaken; and in three cases, the formation and detection of this entity via FAB or MALDI mass spectrometry was achieved. The synthesis of azafullerene pentaadducts C59N(R)5is another recent achievement and the chemical properties of such compounds are currently under investigation. Finally, recent reports on endohedral metalloazafullerenes, azafullerene carbon nanotube peapods and a theoretical study on C59N as an excellent cathode catalyst for hydrogen fuel cells all indicate that unexpected benefits could stem from further research in this area.