Excited-State Aromaticity of Gold(III) Hexaphyrins and Metalation Effect Investigated by Time-Resolved Electronic and Vibrational Spectroscopy |
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| Authors: | Jinseok Kim Dr Juwon Oh Dr Takanori Soya Dr Tomoki Yoneda Dr Seongchul Park Prof Dr Manho Lim Prof Dr Atsuhiro Osuka Prof Dr Dongho Kim |
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| Institution: | 1. Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul, 120-749 Korea;2. Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502 Japan;3. Department of Chemistry and Chemistry Institute for Functional Materials, Pusan National University, Busan, 46241 Korea |
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| Abstract: | Expanded porphyrins with appropriate metalation provide an excellent opportunity to study excited-state aromaticity. The coordinated metal allows the excited-state aromaticity in the triplet state to be detected through the heavy-atom effect, but other metalation effects on the excited-state aromaticity were ambiguous. Herein, the excited-state aromaticity of gold(III) hexaphyrins through the relaxation dynamics was revealed via electronic and vibrational spectroscopy. The SQ states of gold 26]- and 28]-hexaphyrins showed interconvertible absorption and IR spectra with those of counterparts in the ground-state, indicating aromaticity reversal. Furthermore, while the T1 states of gold 28]-hexaphyrins also exhibited reversed aromaticity according to Baird's rule, the ligand-to-metal charge-transfer state of gold 26]-hexaphyrins contributed by the gold metal showed non-aromatic features arising from the odd-number of π-electrons. |
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| Keywords: | Aromatizität Gold Porphyrine Metallierung Zeitaufgelöste IR-Spektroskopie |
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