1. Confinement of an electron in a cuboid molecule
- Subjects
Fluorine compounds -- Chemical properties ,Gas fields -- Chemical properties ,College teachers -- Chemical properties ,Business ,Chemicals, plastics and rubber industries - Abstract
A research group led by Masafumi Sugiyama, a graduate student at the Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo; Project Assistant Professor Midori Akiyama (at the time of the research); Professor Kyoko Nozaki, Takashi Okazoe, a senior research fellow at AGC Inc in joint research with Kenji Komaguchi, Associate Professor, Applied Chemistry Program, Graduate School of Advanced Science and Engineering, Hiroshima University; and Masahiro Higashi, Associate Professor, Molecular Engineering, Graduate School of Engineering, Kyoto University, has for the first time succeeded in synthesizing perfluorocubane, which has fluorine atoms bonded to all vertices and observing an electron confined inside it. The research group has succeeded in synthesizing the world's first perfluorocubane using the PERFECT method developed by AGC Inc. It also succeeded in observing the confinement of an electron inside this molecule. These results provide new possibilities for design guidelines for functional molecules that accept electrons. The results of this research were published online in the journal Science on 11 Aug 2022 (EDT). The group investigated a method to combine multiple fluorine atoms at once by using fluorine gas. In the field of synthetic organic chemistry, fluorine gas has rarely been used because it reacts explosively with organic compounds and is considered difficult to control. In response, AGC Inc has developed the 'PERFECT method,' a technology for introducing fluorine atoms into organic compounds while controlling the reactivity of fluorine gas. In this study, this research group succeeded in simultaneously bonding seven fluorine atoms to cubane by using the PERFECT method. Further chemical reactions introduced the remaining one fluorine atom, achieving the synthesis of perfluorocubane. Single crystal X-ray structure analysis shows that fluorine is introduced at all vertices of cubane. Electrochemical and spectrophotometric measurements demonstrated that, as expected, perfluorocubane has a molecular orbital that can easily accept an electron. The group also irradiated gamma-rays to give an electron to perfluorocubane and observed what chemical species are formed by low-temperature solid-phase matrix isolation ESR method. The results show that the electron given to perfluorocubane is distributed mainly in the inner space of the cuboid. This research is significant in that it overturns the conventional wisdom in that it has developed a molecule that accepts an electron without using a double bond. In the future, the group will further investigate the behaviour and reactivity of the electron confined in perfluorocubane to establish new scientific theories. Because molecules that accept electrons have applications in organic electronic materials, this study is expected to contribute to the development of materials science in the future. Original source: AGC Asahi Glass, website: http://www.agc.com. Copyright Asahi Glass Co Ltd 2022., joint venture; research and development; fluorine; fluorine compounds; fluorine gas; perfluorocubane; [...]
- Published
- 2022