|
|||||
|
|
Double-σ-Bonded Close-Shell Dimers and Peroxy-Linked Open-Shell Dimer Derived from a C3 Symmetric Trioxophenalenyl Neutral Diradical |
|
| Authors: | Dr Tsuyoshi Murata Kenta Yoshida Dr Shuichi Suzuki Dr Akira Ueda Dr Shinsuke Nishida Dr Junya Kawai Dr Kozo Fukui Prof?Dr Kazunobu Sato Prof?Dr Takeji Takui Prof?Dr Kazuhiro Nakasuji Prof?Dr Yasushi Morita |
| Institution: | 1. Department of Applied Chemistry, Faculty of Engineering, Aichi Institute of Technology, Yachigusa 1247, Yakusa, Toyota, Aichi, Japan;2. Department of Chemistry Graduate School of Science, Osaka University, Machikaneyama 1–1, Toyonaka, Osaka, Japan
Contribution: Data curation (lead), Formal analysis (lead), ?Investigation (lead), Methodology (lead);3. Department of Chemistry Graduate School of Engineering Science, Osaka University, Machikaneyama 1–3, Toyonaka, Osaka, Japan;4. Department of Chemistry Faculty of Advanced Science and Technology, Kumamoto University, 2-39-1 Kurokami, Chuo-ku, Kumamoto, Japan;5. Department of Applied Chemistry, Faculty of Engineering, Aichi Institute of Technology, Yachigusa 1247, Yakusa, Toyota, Aichi, Japan Contribution: Data curation (equal), Formal analysis (equal), ?Investigation (equal), Methodology (equal), Writing - original draft (lead);6. Department of Chemistry Graduate School of Science, Osaka University, Machikaneyama 1–1, Toyonaka, Osaka, Japan Contribution: Data curation (equal), Formal analysis (equal), ?Investigation (equal), Methodology (equal);7. Department of Chemistry and Molecular Materials Science Graduate School of Science, Osaka City University/Osaka Metropolitan University, Sugimoto 3–3-138, Sumiyoshi-ku, Osaka, Japan;8. Department of Chemistry Graduate School of Science, Osaka University, Machikaneyama 1–1, Toyonaka, Osaka, Japan Contribution: Conceptualization (lead), Funding acquisition (lead), Project administration (lead), Supervision (lead) |
| Abstract: | A novel neutral diradical of π-extended phenalenyl derivative having three oxo-groups, tri-tert-butyl-1,4,7-trioxophenalenyl, and two types of the corresponding σ-dimers were investigated. Quantum chemical calculations showed that the neutral diradical is in triplet ground state having doubly degenerate singly occupied molecular orbitals. The neutral diradical undergoes a σ-dimerization, generating two types of σ-dimers immediately after the preparation. One of the σ-dimers, which was selectively generated in the crystalline state, was a close-shell dimer linked through double-σ-bonds on the phenalenyl skeleton with a long C?C bond length of 1.66 Å. The other σ-dimer, which existed only in the solution state, was a peroxy-linked open-shell dimer in which one σ-bond was formed between two oxygen atoms. Furthermore, the temperature-dependent 1H NMR and ESR spectra revealed that these σ-dimers are in equilibrium in the solution state by the reversible σ-bond formation/cleavage via the neutral diradical as a key intermediate. |
| Keywords: | DFT calculations EPR spectroscopy neutral diradical oxophenalenoxyl σ-dimer |