Ligand-to-metal charge transfer driven by excited-state antiaromaticity in metallohexaphyrins
- Authors
- Kim, Jinseok; Kim, Hyeonwoo; Oh, Juwon; Kim, Dongho
- Issue Date
- Apr-2022
- Publisher
- 대한화학회
- Keywords
- aromaticity; Baird rule; excited-state antiaromaticity; ligand-to-metal charge transfer; metallohexaphyrin
- Citation
- Bulletin of the Korean Chemical Society, v.43, no.4, pp 508 - 513
- Pages
- 6
- Journal Title
- Bulletin of the Korean Chemical Society
- Volume
- 43
- Number
- 4
- Start Page
- 508
- End Page
- 513
- URI
- https://scholarworks.bwise.kr/sch/handle/2021.sw.sch/20647
- DOI
- 10.1002/bkcs.12483
- ISSN
- 0253-2964
1229-5949
- 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 S-0 state become antiaromatic in the S-1 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 S-0-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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