Modulations of a Metal-Ligand Interaction and Photophysical Behaviors by Huckel-Mobius Aromatic Switching
- Authors
- Kim, Jinseok; Oh, Juwon; Park, Seongchul; Yoneda, Tomoki; Osuka, Atsuhiro; Lim, Manho; Kim, Dongho
- Issue Date
- 12-Jan-2022
- Publisher
- American Chemical Society
- Citation
- Journal of the American Chemical Society, v.144, no.1, pp 582 - 589
- Pages
- 8
- Journal Title
- Journal of the American Chemical Society
- Volume
- 144
- Number
- 1
- Start Page
- 582
- End Page
- 589
- URI
- https://scholarworks.bwise.kr/sch/handle/2021.sw.sch/20195
- DOI
- 10.1021/jacs.1c11705
- ISSN
- 0002-7863
1520-5126
- Abstract
- In organometallic complexes containing pi-conjugated macrocyclic chelate ligands, conformational change significantly affects metal-ligand electronic interactions, hence tuning properties of the complexes. In this regard, we investigated the metal-ligand interactions in hexaphyrin mono-Pd(II) complexes Pd[28]M and Pd[26]H, which exhibit a redox-induced switching of Huckel-Mobius aromaticity and subsequent molecular conformation, and their effect on the electronic structure and photophysical behaviors. In Mobius aromatic Pd[28]M, the weak metal-ligand interaction leads to the pi electronic structure of the hexaphyrin ligand remaining almost intact, which undergoes efficient intersystem crossing (ISC) assisted by the heavy-atom effect of the Pd metal. In Huckel aromatic Pd[26]H, the significant metal-ligand interaction results in ligand-to-metal charge-transfer (LMCT) in the excited-state dynamics. These contrasting metal-ligand electronic interactions have been revealed by time-resolved electronic and vibrational spectroscopies and time-dependent DFT calculations. This work indicates that the conspicuous modulation of metal-ligand interaction by Huckel-Mobius aromaticity switching is an appealing approach to manipulate molecular properties of metal complexes, further enabling the fine-tuning of metal-ligand interactions and the novel design of functional organometallic materials.
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