Excited-State Aromaticity of Gold(III) Hexaphyrins and Metalation Effect Investigated by Time-Resolved Electronic and Vibrational Spectroscopy

Jinseok Kim; Juwon Oh; Takanori Soya; Tomoki Yoneda; Seongchul Park; Manho Lim; Atsuhiro Osuka; Dongho Kim

doi:10.1002/anie.201913058

Excited-State Aromaticity of Gold(III) Hexaphyrins and Metalation Effect Investigated by Time-Resolved Electronic and Vibrational Spectroscopy

Jinseok Kim, Juwon Oh, Takanori Soya, Tomoki Yoneda, Seongchul Park, Manho Lim, Atsuhiro Osuka, Dongho Kim

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

10 Citations (Scopus)

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 S_Q 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.

Original language	English
Pages (from-to)	5129-5134
Number of pages	6
Journal	Angewandte Chemie - International Edition
Volume	59
Issue number	13
DOIs	https://doi.org/10.1002/anie.201913058
Publication status	Published - 2020 Mar 23

Bibliographical note

Funding Information:
The work at Yonsei University was supported by Strategic Research (NRF2016R1E1A1A01943379) through the National Research Foundation of Korea (NRF) funded by the Ministry of Science. The quantum calculations were performed with the supercomputing resources of the Korea Institute of Science and Technology Information. The work at Kyoto University was supported by JSPS KAKENHI Grant Numbers (JP18K19074 and JP18H03910). T.S. and T.Y. acknowledge JSPS Fellowships for Young Scientists. The work in Pusan National University was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MEST) 55 (NRF-2017R1A2A2A05001052).

Funding Information:
The work at Yonsei University was supported by Strategic Research (NRF2016R1E1A1A01943379) through the National Research Foundation of Korea (NRF) funded by the Ministry of Science. The quantum calculations were performed with the supercomputing resources of the Korea Institute of Science and Technology Information. The work at Kyoto University was supported by JSPS KAKENHI Grant Numbers (JP18K19074 and JP18H03910). T.S. and T.Y. acknowledge JSPS Fellowships for Young Scientists. The work in Pusan National University was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MEST) 55 (NRF‐2017R1A2A2A05001052).

Publisher Copyright:
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)

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10.1002/anie.201913058

Cite this

@article{2b950322a8384bf3a03359001fc154b7,

title = "Excited-State Aromaticity of Gold(III) Hexaphyrins and Metalation Effect Investigated by Time-Resolved Electronic and Vibrational Spectroscopy",

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.",

author = "Jinseok Kim and Juwon Oh and Takanori Soya and Tomoki Yoneda and Seongchul Park and Manho Lim and Atsuhiro Osuka and Dongho Kim",

note = "Funding Information: The work at Yonsei University was supported by Strategic Research (NRF2016R1E1A1A01943379) through the National Research Foundation of Korea (NRF) funded by the Ministry of Science. The quantum calculations were performed with the supercomputing resources of the Korea Institute of Science and Technology Information. The work at Kyoto University was supported by JSPS KAKENHI Grant Numbers (JP18K19074 and JP18H03910). T.S. and T.Y. acknowledge JSPS Fellowships for Young Scientists. The work in Pusan National University was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MEST) 55 (NRF-2017R1A2A2A05001052). Funding Information: The work at Yonsei University was supported by Strategic Research (NRF2016R1E1A1A01943379) through the National Research Foundation of Korea (NRF) funded by the Ministry of Science. The quantum calculations were performed with the supercomputing resources of the Korea Institute of Science and Technology Information. The work at Kyoto University was supported by JSPS KAKENHI Grant Numbers (JP18K19074 and JP18H03910). T.S. and T.Y. acknowledge JSPS Fellowships for Young Scientists. The work in Pusan National University was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MEST) 55 (NRF‐2017R1A2A2A05001052). Publisher Copyright: {\textcopyright} 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

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AU - Kim, Jinseok

AU - Oh, Juwon

AU - Soya, Takanori

AU - Yoneda, Tomoki

AU - Park, Seongchul

AU - Lim, Manho

AU - Osuka, Atsuhiro

AU - Kim, Dongho

N1 - Funding Information: The work at Yonsei University was supported by Strategic Research (NRF2016R1E1A1A01943379) through the National Research Foundation of Korea (NRF) funded by the Ministry of Science. The quantum calculations were performed with the supercomputing resources of the Korea Institute of Science and Technology Information. The work at Kyoto University was supported by JSPS KAKENHI Grant Numbers (JP18K19074 and JP18H03910). T.S. and T.Y. acknowledge JSPS Fellowships for Young Scientists. The work in Pusan National University was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MEST) 55 (NRF-2017R1A2A2A05001052). Funding Information: The work at Yonsei University was supported by Strategic Research (NRF2016R1E1A1A01943379) through the National Research Foundation of Korea (NRF) funded by the Ministry of Science. The quantum calculations were performed with the supercomputing resources of the Korea Institute of Science and Technology Information. The work at Kyoto University was supported by JSPS KAKENHI Grant Numbers (JP18K19074 and JP18H03910). T.S. and T.Y. acknowledge JSPS Fellowships for Young Scientists. The work in Pusan National University was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MEST) 55 (NRF‐2017R1A2A2A05001052). Publisher Copyright: © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2020/3/23

Y1 - 2020/3/23

N2 - 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.

AB - 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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Excited-State Aromaticity of Gold(III) Hexaphyrins and Metalation Effect Investigated by Time-Resolved Electronic and Vibrational Spectroscopy

Abstract

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