Ligand-to-metal charge transfer driven by excited-state antiaromaticity in metallohexaphyrins

Jinseok Kim; Hyeonwoo Kim; Juwon Oh; Dongho Kim

doi:10.1002/bkcs.12483

Ligand-to-metal charge transfer driven by excited-state antiaromaticity in metallohexaphyrins

Jinseok Kim, Hyeonwoo Kim, Juwon Oh, Dongho Kim

Department of Chemistry

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

Abstract

We investigated the effect of excited-state antiaromaticity on the ligand-to-metal charge transfer (LMCT) process of metallohexaphyrins. According to Baird rule, the aromatic metallohexaphyrins in the S₀ state become antiaromatic in the S₁ state. Because of the metal–ligand redox-like nature of LMCT process, the LMCT process can release the antiaromatic nature and its energetic destabilization. The metallohexaphyrins show a correlation between the S₀-state aromaticity and time constants for the LMCT process, which well demonstrates that the excited-state antiaromaticity at the Franck–Condon state acts as a driving force for the LMCT process. These findings elucidate the effect of excited-state antiaromaticity on the excited-state behaviors and further provide an insight into the photochemistry of organic molecules.

Original language	English
Pages (from-to)	508-513
Number of pages	6
Journal	Bulletin of the Korean Chemical Society
Volume	43
Issue number	4
DOIs	https://doi.org/10.1002/bkcs.12483
Publication status	Published - 2022 Apr

Bibliographical note

Funding Information:
Soonchunhyang University, Grant/Award Number: 20201140; National Research Foundation of Korea, Grant/Award Numbers: 2021R1A6A1A03039503, 2021R1C1C1013828 Funding information

Funding Information:
The work was supported by National Research Foundation of Korea (NRF) grant funded by the Korea government (No. 2021R1C1C1013828 and No. 2021R1A6A1A03039503) and the Soonchunhyang University Research Fund (No. 20201140).

Publisher Copyright:
© 2022 Korean Chemical Society, Seoul & Wiley-VCH GmbH.

All Science Journal Classification (ASJC) codes

Chemistry(all)

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10.1002/bkcs.12483

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title = "Ligand-to-metal charge transfer driven by excited-state antiaromaticity in metallohexaphyrins",

abstract = "We investigated the effect of excited-state antiaromaticity on the ligand-to-metal charge transfer (LMCT) process of metallohexaphyrins. According to Baird rule, the aromatic metallohexaphyrins in the S0 state become antiaromatic in the S1 state. Because of the metal–ligand redox-like nature of LMCT process, the LMCT process can release the antiaromatic nature and its energetic destabilization. The metallohexaphyrins show a correlation between the S0-state aromaticity and time constants for the LMCT process, which well demonstrates that the excited-state antiaromaticity at the Franck–Condon state acts as a driving force for the LMCT process. These findings elucidate the effect of excited-state antiaromaticity on the excited-state behaviors and further provide an insight into the photochemistry of organic molecules.",

author = "Jinseok Kim and Hyeonwoo Kim and Juwon Oh and Dongho Kim",

note = "Funding Information: Soonchunhyang University, Grant/Award Number: 20201140; National Research Foundation of Korea, Grant/Award Numbers: 2021R1A6A1A03039503, 2021R1C1C1013828 Funding information Funding Information: The work was supported by National Research Foundation of Korea (NRF) grant funded by the Korea government (No. 2021R1C1C1013828 and No. 2021R1A6A1A03039503) and the Soonchunhyang University Research Fund (No. 20201140). Publisher Copyright: {\textcopyright} 2022 Korean Chemical Society, Seoul & Wiley-VCH GmbH.",

year = "2022",

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doi = "10.1002/bkcs.12483",

language = "English",

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AU - Oh, Juwon

AU - Kim, Dongho

N1 - Funding Information: Soonchunhyang University, Grant/Award Number: 20201140; National Research Foundation of Korea, Grant/Award Numbers: 2021R1A6A1A03039503, 2021R1C1C1013828 Funding information Funding Information: The work was supported by National Research Foundation of Korea (NRF) grant funded by the Korea government (No. 2021R1C1C1013828 and No. 2021R1A6A1A03039503) and the Soonchunhyang University Research Fund (No. 20201140). Publisher Copyright: © 2022 Korean Chemical Society, Seoul & Wiley-VCH GmbH.

PY - 2022/4

Y1 - 2022/4

N2 - We investigated the effect of excited-state antiaromaticity on the ligand-to-metal charge transfer (LMCT) process of metallohexaphyrins. According to Baird rule, the aromatic metallohexaphyrins in the S0 state become antiaromatic in the S1 state. Because of the metal–ligand redox-like nature of LMCT process, the LMCT process can release the antiaromatic nature and its energetic destabilization. The metallohexaphyrins show a correlation between the S0-state aromaticity and time constants for the LMCT process, which well demonstrates that the excited-state antiaromaticity at the Franck–Condon state acts as a driving force for the LMCT process. These findings elucidate the effect of excited-state antiaromaticity on the excited-state behaviors and further provide an insight into the photochemistry of organic molecules.

AB - We investigated the effect of excited-state antiaromaticity on the ligand-to-metal charge transfer (LMCT) process of metallohexaphyrins. According to Baird rule, the aromatic metallohexaphyrins in the S0 state become antiaromatic in the S1 state. Because of the metal–ligand redox-like nature of LMCT process, the LMCT process can release the antiaromatic nature and its energetic destabilization. The metallohexaphyrins show a correlation between the S0-state aromaticity and time constants for the LMCT process, which well demonstrates that the excited-state antiaromaticity at the Franck–Condon state acts as a driving force for the LMCT process. These findings elucidate the effect of excited-state antiaromaticity on the excited-state behaviors and further provide an insight into the photochemistry of organic molecules.

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Ligand-to-metal charge transfer driven by excited-state antiaromaticity in metallohexaphyrins

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