Open-Cage Fullerenes: Synthesis, Structure, and Molecular Encapsulation
Open-Cage Fullerenes: Synthesis, Structure, and Molecular Encapsulation
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DOI：
10.1002/chin.200552235
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发表时间：
2005-09
期刊：
影响因子：
--
通讯作者：
S. Iwamatsu;S. Murata
中科院分区：
文献类型：
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作者：
S. Iwamatsu;S. Murata
富勒烯笼的碳-碳键断裂提供了在富勒烯表面上具有开口的开笼富勒烯衍生物。本文综述了近年来开笼C60衍生物的合成及其分子包封性能的研究进展。C60的环己二烯衍生物的光化学重排生成笼状断裂的前体双（富勒烯）.双（富勒烯）的光氧化碳-碳键断裂提供具有12元环的开笼二酮衍生物。二酮衍生物与芳族肼或腙的反应允许通过区域选择性笼状断裂的孔的环膨胀，以产生带有16元环的产物。产物中的孔足够大以使氢分子通过，从而产生内嵌氢复合物。在与邻苯二胺反应的情况下，两个碳-碳键依次断裂，得到具有20元环孔的产物。该产物自发地包封一个水分子以形成一个内包合的水复合物。
The carbon-carbon bond scission of the fullerene cage offers an open-cage fullerene derivative having an opening on the fullerene surface. This account summarizes our recent studies on the syntheses of open-cage C 6 0 derivatives as well as their properties of molecular encapsulation. The photochemical rearrangement of the cyclohexadiene derivative of C 6 0 gives bis(fulleroid), the precursor for the cage scission. The photooxygenative carbon-carbon bond cleavage of bis(fulleroid) affords an open-cage diketone derivative having a 12-membered ring. The reaction of the diketone derivative with aromatic hydrazine or hydrazone allows the ring expansion of the orifice by regioselective cage scission to yield a product bearing a 16-membered ring. The orifice in the product is large enough to pass a hydrogen molecule producing an endohedral hydrogen complex. In the case of the reaction with ortho-phenylenediamine, two carbon-carbon bonds are sequentially cleaved to afford a product having a 20-membered ring orifice. This product spontaneously encapsulates one water molecule to form an endohedral water complex.