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Hokkaido University Collection of Scholarly and Academic Papers >
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Flexible C-C Bonds: Reversible Expansion, Contraction, Formation, and Scission of Extremely Elongated Single Bonds
| Title: | Flexible C-C Bonds: Reversible Expansion, Contraction, Formation, and Scission of Extremely Elongated Single Bonds |
| Authors: | Shimajiri, Takuya Browse this author | | Suzuki, Takanori Browse this author | | Ishigaki, Yusuke Browse this author →KAKEN DB |
| Keywords: | cyclization | | long bonds | | redox chemistry | | single-crystal-to-single-crystal transformations | | thermal cycloreversion |
| Issue Date: | 1-Dec-2020 |
| Publisher: | Wiley-Blackwell |
| Journal Title: | Angewandte chemie-international edition |
| Volume: | 59 |
| Issue: | 49 |
| Start Page: | 22252 |
| End Page: | 22257 |
| Publisher DOI: | 10.1002/anie.202010615 |
| Abstract: | Since carbon-carbon (C-C) covalent bonds are rigid and robust, the bond length is, in general, nearly constant and depends only on the bond order and hybrid orbitals. We report herein direct visualization of the reversible expansion and contraction of a C(sp(3))-C(sp(3)) single bond by light and heat. This flexibility of a C-C bond was demonstrated by X-ray analysis and Raman spectroscopy of hexaphenylethane (HPE)-type hydrocarbons with two spiro-dibenzocycloheptatriene units, the intramolecular [2+2] photocyclization of which and thermal cleavage of the resulting cyclobutane ring both occur in a single-crystalline phase. The force constant of the contracted C-C bond is 1.6 times greater than that of the expanded bond. Since formation of the cyclobutane ring and contraction of the C-C bond lower the HOMO level by approximately 1 eV, the oxidative properties of these HPEs with a flexible C-C bond can be deactivated/activated by light/heat. |
| Rights: | This is the peer reviewed version of the following article: Angewandte Chemie (International ed.) 59(49) December 1, 2020 pp.22252-22257
, which has been published in final form at https://doi.org/10.1002/anie.202010615. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. |
| Type: | article (author version) |
| URI: | http://hdl.handle.net/2115/83376 |
| Appears in Collections: | 理学院・理学研究院 (Graduate School of Science / Faculty of Science) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)
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Submitter: 石垣 侑祐
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