Internally 2,5-Thienylene-Bridged [46]Decaphyrin: (Annuleno)annulene Network Consisting of Möbius Aromatic Thia[28]hexaphyrins and Strong Hückel Aromaticity of its Protonated Form
Takanori Soya
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502 Japan
Search for more papers by this authorDr. Hirotaka Mori
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502 Japan
Search for more papers by this authorYongseok Hong
Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul, 120-749 Korea
Search for more papers by this authorYun Hee Koo
Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul, 120-749 Korea
Search for more papers by this authorCorresponding Author
Prof. Dr. Dongho Kim
Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul, 120-749 Korea
Search for more papers by this authorCorresponding Author
Prof. Dr. Atsuhiro Osuka
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502 Japan
Search for more papers by this authorTakanori Soya
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502 Japan
Search for more papers by this authorDr. Hirotaka Mori
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502 Japan
Search for more papers by this authorYongseok Hong
Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul, 120-749 Korea
Search for more papers by this authorYun Hee Koo
Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul, 120-749 Korea
Search for more papers by this authorCorresponding Author
Prof. Dr. Dongho Kim
Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul, 120-749 Korea
Search for more papers by this authorCorresponding Author
Prof. Dr. Atsuhiro Osuka
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502 Japan
Search for more papers by this authorGraphical Abstract
Switching aromaticity: 1,3-Phenylene- and 2,5-thienylene-bridged [46]decaphyrins A and B have been synthesized. While A shows Hückel-aromatic character derived from its global 46π-conjugated circuit, B displays an (annuleno)annulene-type structure consisting of two twisted Möbius-aromatic thia[28]hexaphyrins. Upon protonation, these [46]decaphyrins undergo large structural changes and become strongly aromatic.
Abstract
Internally 1,3-phenylene- and 2,5-thienylene-bridged [46]decaphyrins 2 and 3 have been synthesized. While 2 shows modest aromatic character derived from the global 46π-conjugated circuit, 3 displays larger aromatic character owing to the contribution of an (annuleno)annulene-type network consisting of two twisted Möbius aromatic thia[28]hexaphyrin segments in addition to the global 46π-network. Upon protonation, these [46]decaphyrins underwent large structural changes to acquire strong aromaticity. Protonated 3 has been revealed to take on a planar structure composed of fused two triangular thia[28]hexaphyrin segments.
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