Per-Substituted [8]Circulene and Its Non-Planar Fragments: Synthesis, Structural Analysis, and Properties

Chieh Ning Feng, Wen Ching Hsu, Jen Yi Li, Ming Yu Kuo, Yao-Ting Wu

研究成果: Article

13 引文 斯高帕斯(Scopus)


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.

頁(從 - 到)9198-9208
期刊Chemistry - A European Journal
出版狀態Published - 2016 一月 1


All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry