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Modulation of Energy Conversion Processes in Carbonaceous Molecular Bearings |
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| Authors: | Dr. Shunpei Hitosugi Prof. Kei Ohkubo Yuki Kawashima Dr. Taisuke Matsuno Sho Kamata Kosuke Nakamura Hirohiko Kono Dr. Sota Sato Prof. Shunichi Fukuzumi Prof. Hiroyuki Isobe |
| Affiliation: | 1. Department of Chemistry, Tohoku University, Aoba-ku, Sendai, Japan;2. Department of Material and Life Science, Graduate School of Engineering, Osaka University, ALCA and SENTAN, JST, Osaka, Japan;3. Department of Chemistry and Nano Science, Ewha Womans University, Seoul, Korea;4. Advanced Institute for Materials Research (AIMR) and, JST, ERATO, Isobe Degenerate π-Integration Project, Tohoku University, Aoba-ku, Sendai, Japan;5. Faculty of Science and Technology, Meijo University, ALCA and SENTAN, JST, Shiogamaguchi, Tempaku, Nagoya, Aichi, Japan |
| Abstract: | The energetics and photodynamics of carbonaceous molecular bearings with discrete molecular structures were investigated. A series of supramolecular bearings comprising belt‐persistent tubular cycloarylene and fullerene molecules accepted photonic stimuli to afford charge‐separated species via a photoinduced electron transfer process. The energy conversion processes associated with the photoexcitation, however, differed depending on the molecular structure. A π‐lengthened tubular molecule allowed for the emergence of an intermediary triplet excited state at the bearing, which should lead to an energy conversion to thermal energy. On the other hand, low‐lying charge‐separated species induced by an endohedral lithium ion in fullerene enabled back electron transfer processes to occur without involving triplet excited species. The structure–photodynamics relationship was analyzed in terms of the Marcus theory to reveal a large electronic coupling in this dynamic supramolecular system. |
| Keywords: | electron transfer fullerenes molecular bearings nanotubes peapods |