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- Title
Per-Substituted [8]Circulene and Its Non-Planar Fragments: Synthesis, Structural Analysis, and Properties.
- Authors
Feng, Chieh ‐ Ning; Hsu, Wen ‐ Ching; Li, Jen ‐ Yi; Kuo, Ming ‐ Yu; Wu, Yao ‐ Ting
- 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.
- Subjects
STRUCTURAL analysis (Science); BIOCONJUGATES; REDSHIFT; PHOTOPHORES; STRUCTURAL analysis (Engineering)
- Publication
Chemistry - A European Journal, 2016, Vol 22, Issue 27, p9198
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201600124