title: Per-Substituted [8]Circulene and Its Non-Planar Fragments: Synthesis, Structural Analysis, and Properties.
abstract: The syntheses, structures, and physical properties of a full series of benzannulated tetraphenylenes are reported. The palladium-catalyzed annulation of tetraiodo-substituted 2,3,6,7,10,11,14,15-octamethyltetraphenylene with insufficient di(4-anisyl)ethyne yielded a mixture of per-substituted [8]circulene and its non-planar fragments, including mono-, para-di-, ortho-di-, and triannulated products. Their structures were unambiguously verified by X-ray crystallography. Successive benzannulations significantly affect the molecular geometries, dynamic behaviors, and physical properties of the compounds. In this series of compounds, [8]circulene is the most strained one, as reflected by the significant deplanarization of the phenanthrene moieties (ca. 63° in the bay region) and the fact that it has the highest strain energy (120.6 kcal mol(-1) ). The dynamic behaviors of these compounds were examined both experimentally and theoretically. The ring flipping of per-substituted [8]circulene is confirmed to proceed through pseudorotation with a barrier of around 21 kcal mol(-1) , whereas its non-planar fragments require much more energy for the ring inversion. The photophysical and electrochemical properties of the investigated compounds depend strongly on the extent of efficient π conjugation. The successive benzannulations red-shift both the absorption and the emission bands, and reduce the first oxidation potential.
authors.affiliation: Department of Chemistry, National Cheng Kung University, No.1 Ta-Hsueh Road, 70101, Tainan, Taiwan.
authors.forename: Chieh-Ning
authors.initials: CN
authors.lastname: Feng
authors.affiliation: Department of Chemistry, National Cheng Kung University, No.1 Ta-Hsueh Road, 70101, Tainan, Taiwan.
authors.forename: Wen-Ching
authors.initials: WC
authors.lastname: Hsu
authors.affiliation: Department of Chemistry, National Cheng Kung University, No.1 Ta-Hsueh Road, 70101, Tainan, Taiwan.
authors.forename: Jen-Yi
authors.initials: JY
authors.lastname: Li
authors.affiliation: Department of Applied Chemistry, National Chi Nan University, No. 1 University Rd., 54561 Puli, Nantou, Taiwan.
authors.forename: Ming-Yu
authors.initials: MY
authors.lastname: Kuo
authors.affiliation: Department of Chemistry, National Cheng Kung University, No.1 Ta-Hsueh Road, 70101, Tainan, Taiwan. ytwuchem@mail.ncku.edu.tw.
authors.forename: Yao-Ting
authors.initials: YT
authors.lastname: Wu
keywords: circulenes; density functional calculations; palladium; pseudorotation; tetraphenylenes