Synthesis, Structures, and Optical Properties of Azahelicene Derivatives and Unexpected Formation of Azaheptacirculenes.
['Chen F', 'Tanaka T', 'Mori T', 'Osuka A']
Chemistry. 2018 Mar 13. doi: 10.1002/chem.201800617. [Epub ahead of print]
['JAPAN.', 'Graduate School of Science, Kyoto University, Chemistry, Kitashirakawa Oiwake-cho, 606-8502, Kyoto, JAPAN.', 'Graduate School of Engineering, Osaka University, Department of Applied Chemistry, 2-1 Yamada-oka, 565-0871, Suita, JAPAN.', 'Kyoto University, JAPAN.']
['Polycyclic heteroaromatic compounds including pyrrole units are promising functional scaffolds owing to their electron-rich nature, bright fluorescence, and applicability to anion recognition at the pyrrolic hydrogen. We report herein the effective synthesis of pseudo-azahelicene and azahelicene derivatives, and unexpected formation of azaheptacirculenes by oxidative fusion reactions. By choosing reaction conditions and peripheral substituents attached at the terminal indole moieties, we obtained azahelicenes 10a-c and azaheptacirculenes 11a,c selectively in moderate to good yields. Their solid-state structures have been revealed by X-ray diffraction analysis. UV/Vis absorption, emission, and cyclic voltammetry of these compounds were studied in comparison with those of previously reported tetraazacirculene (TA8C), a symmetric and planar molecule. Furthermore, the enantiomeric separation of dimethyl-substituted azahelicene 10b was achieved, and the racemization kinetics have been elucidated both theoretically and experimentally. This work illustrates a wealth of advantages of pyrrole incorporation into the polycyclic aromatic scaffolds in terms of synthetic aspects, structural variation and optical tuning.']