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Preparation of a Corannulene-functionalized Hexahelicene by CopperI-catalyzed Alkyne-azide Cycloaddition of Nonplanar Polyaromatic Units
Published on: September 18, 2016
Cyclopenta-fused polyaromatic hydrocarbons: synthesis and characterisation of a stable, carbon-centred helical
Stefan Herzog1, Alexander Hinz2, Frank Breher2
1Institut für Organische Chemie, Karlsruher Institut für Technologie (KIT), 76131 Karlsruhe, Fritz-Haber-Weg 6, Germany.
Abstract:
An air- and moisture-stable helical radical with seven six- and five-membered rings arranged alternately was synthesized by cyclizations in a suitably ortho,ortho'-substituted terphenyl and re-establishment of its conjugation. Mesityl groups at the five-membered rings prevent radical reactions. This cyclopenta-fused polyaromatic hydrocarbon (CP-PAH) was characterized by X-ray crystallographic analysis, EPR and UV/Vis spectroscopy, and by cyclic voltammetry. Further properties and spectra were determined by quantum chemical calculation (spin densities, orbital energies, UV/Vis/NIR and ECD spectra). It turned out that this radical is best described with its radical centre being in the outer five-membered rings, which allows for the largest number of fully intact benzene rings. Its triradical character is rather small and can be neglected. The five-membered rings show significant antiaromatic character, which is highest in the central ring.
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