Sugiyama Masafumi, Akiyama Midori, Yonezawa Yuki, Komaguchi Kenji, Higashi Masahiro, Nozaki Kyoko, Okazoe Takashi
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, Bunkyo-ku, Tokyo 113-8656, Japan.
Department of Applied Chemistry, Graduate School of Advanced Science and Engineering, Hiroshima University, Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8527, Japan.
Science. 2022 Aug 12;377(6607):756-759. doi: 10.1126/science.abq0516. Epub 2022 Aug 11.
Fluorinated analogs of polyhedral hydrocarbons have been predicted to localize an electron within their cages upon reduction. Here, we report the synthesis and characterization of perfluorocubane, a stable polyhedral fluorocarbon. The key to the successful synthesis was the efficient introduction of multiple fluorine atoms to cubane by liquid-phase reaction with fluorine gas. The solid-state structure of perfluorocubane was confirmed using x-ray crystallography, and its electron-accepting character was corroborated electrochemically and spectroscopically. The radical anion of perfluorocubane was examined by matrix-isolation electron spin resonance spectroscopy, which revealed that the unpaired electron accepted by perfluorocubane is located predominantly inside the cage.
据预测，多面体碳氢化合物的氟化类似物在还原时会将一个电子定位在其笼状结构内。在此，我们报告了全氟立方烷（一种稳定的多面体氟碳化合物）的合成与表征。成功合成的关键在于通过与氟气的液相反应将多个氟原子高效引入立方烷中。利用X射线晶体学确定了全氟立方烷的固态结构，并通过电化学和光谱学方法证实了其电子接受特性。通过基质隔离电子自旋共振光谱对全氟立方烷的自由基阴离子进行了研究，结果表明全氟立方烷接受的未成对电子主要位于笼状结构内部。
