title: 9,10-Diaminoanthracenes Revisited: The Influence of N-Substituents on Their Electronic States.
abstract: The electronic and molecular structures of 9,10-diamino-substituted anthracenes with different N-substituents have been re-examined. In particular, different N-substituents influence both the electronic and molecular structures of the oxidized species of 9,10-diaminoanthracenes. The anthrylene moiety of 9,10-bis(N,N-di(p-anisyl)amino)anthracene retains its planarity during the course of two successive one-electron oxidations, whereas 9,10-bis(N,N-dimethylamino)anthracene and 9,10-bis(N-p-anisyl-N-methylamino)anthracene undergo a substantial structural change to a butterfly-like structure through a two-electron oxidation process. The structural changes observed for the oxidized states are ascribed to significant differences in the frontier molecular orbitals of the above-mentioned three kinds of 9,10-diaminoanthracenes due to different extents of mixing between the amine-localized and anthrylene-localized orbitals.
authors.affiliation: Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto, 615-8510, Japan.
authors.forename: Masashi
authors.initials: M
authors.lastname: Uebe
authors.affiliation: Institute for Liberal Arts and Sciences, Kyoto University, Kyoto, 606-8501, Japan.
authors.forename: Tatsuhisa
authors.initials: T
authors.lastname: Kato
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
authors.affiliation: Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto, 615-8510, Japan.
authors.forename: Akihiro
authors.identifier: http://orcid.org/0000-0002-8698-0032
authors.initials: A
authors.lastname: Ito
keywords: UV/Vis spectroscopy; acenes; arylamines; density functional calculations; electrochemistry