Department of Mechanical Engineering, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8565, Japan.
Chem Commun (Camb). 2018 Oct 4;54(80):11244-11259. doi: 10.1039/c8cc05965a.
Fullerene cations, namely [60]fullerene radical cation (C60˙+) and organo[60]fullerenyl cation (RC60+), are less investigated as intermediates in synthetic fullerene chemistry because of the intrinsic electronegativity of C60. Remarkably, these two intermediates can mediate reactions that afford versatile, unique and unexpected fullerene derivatives. This review article mainly describes these C60˙+ and RC60+ intermediates and includes a variety of topics, from the generation of C60˙+ and RC60+ species to their applications in fullerene modification reactions, such as Friedel-Crafts hydroarylation, nucleophilic addition, dimerization, intramolecular rearrangement reactions, and intramolecular cyclization reactions. Additionally, this review deeply discusses the mechanism of the formation of unique [60]fullerene derivatives involving [60]fullerene radical cation and organo[60]fullerenyl cation intermediates. In addition, the electrochemical properties and photovoltaic performance of these fullerene derivatives produced through C60˙+ or RC60+-mediated reactions are discussed in this review.
富勒烯阳离子，即[60]富勒烯自由基阳离子（C60˙+）和有机[60]富勒烯阳离子（RC60+），由于 C60 的固有电负性，作为合成富勒烯化学中的中间体研究较少。值得注意的是，这两种中间体可以介导反应，从而提供多样、独特和意想不到的富勒烯衍生物。本文主要描述了这些 C60˙+和 RC60+中间体，并包括了各种主题，从 C60˙+和 RC60+物种的生成到它们在富勒烯修饰反应中的应用，如 Friedel-Crafts 酰基化、亲核加成、二聚化、分子内重排反应和分子内环化反应。此外，本文还深入讨论了涉及[60]富勒烯自由基阳离子和有机[60]富勒烯阳离子中间体的独特[60]富勒烯衍生物形成的机制。此外，本文还讨论了通过 C60˙+或 RC60+-介导的反应生成的这些富勒烯衍生物的电化学性质和光伏性能。
