title: A Triphenylamine with Two Phenoxy Radicals Having Unusual Bonding Patterns and a Closed-Shell Electronic State.
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.
authors.affiliation: Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510 (Japan). d.sakamaki@chem.eng.osaka-u.ac.jp.|Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871 (Japan). d.sakamaki@chem.eng.osaka-u.ac.jp.
authors.forename: Daisuke
authors.initials: D
authors.lastname: Sakamaki
authors.affiliation: Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510 (Japan).
authors.forename: Soichiro
authors.initials: S
authors.lastname: Yano
authors.affiliation: Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510 (Japan).|Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871 (Japan).
authors.forename: Toshiyuki
authors.initials: T
authors.lastname: Kobashi
authors.affiliation: Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510 (Japan). seki@moleng.kyoto-u.ac.jp.|Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871 (Japan). seki@moleng.kyoto-u.ac.jp.
authors.forename: Shu
authors.initials: S
authors.lastname: Seki
authors.affiliation: Department of Materials Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510 (Japan).
authors.forename: Takuya
authors.initials: T
authors.lastname: Kurahashi
authors.affiliation: Department of Materials Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510 (Japan).
authors.forename: Seijiro
authors.initials: S
authors.lastname: Matsubara
authors.affiliation: Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510 (Japan). aito@scl.kyoto-u.ac.jp.
authors.forename: Akihiro
authors.initials: A
authors.lastname: Ito
authors.affiliation: Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510 (Japan).
authors.forename: Kazuyoshi
authors.initials: K
authors.lastname: Tanaka
keywords: conjugation; density functional calculations; electronic structure; radicals; structure elucidation