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A Triphenylamine with Two Phenoxy Radicals Having Unusual Bonding Patterns and a Closed‐Shell Electronic State |
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| Authors: | Dr. Daisuke Sakamaki Soichiro Yano Toshiyuki Kobashi Prof. Dr. Shu Seki Dr. Takuya Kurahashi Prof. Dr. Seijiro Matsubara Dr. Akihiro Ito Prof. Dr. Kazuyoshi Tanaka |
| Affiliation: | 1. Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo‐ku, Kyoto 615‐8510 (Japan);2. Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565‐0871 (Japan);3. Department of Materials Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo‐ku, Kyoto 615‐8510 (Japan) |
| Abstract: | Reported herein is the structure and the electronic properties of a novel triphenylamine derivative having two phenoxy radicals appended to the amino nitrogen atom. X‐ray single crystal analysis and the magnetic resonance measurements demonstrates the unexpected closed‐shell electronic structure, even at room temperature, of the molecule and two unusual C? N bonds with multiple‐bond character. The theoretical calculations support the experimentally determined molecular geometry with the closed‐shell electronic structure, and predicted a small HOMO–LUMO gap originating from the nonbonding character of the HOMO. The optical and electrochemical measurements show that the molecule has a remarkably small HOMO–LUMO gap compared with its triphenylamine precursor. |
| Keywords: | conjugation density functional calculations electronic structure radicals structure elucidation |