Synthesis of Subporphyrin Free Bases
- Authors
- Liu, Le; Kim, Jinseok; Xu, Ling; Rao, Yutao; Zhou, Mingbo; Yin, Bangshao; Oh, Juwon; Kim, Dongho; Osuka, Atsuhiro; Song, Jianxin
- Issue Date
- Dec-2022
- Publisher
- John Wiley & Sons Ltd.
- Keywords
- B-III-Subpoprhyrin; Subporphyrin Free Base; Subporphyrin Free Base Dimer; Subporphyrinoid; Suzuki-Miyaura Coupling
- Citation
- Angewandte Chemie International Edition, v.61, no.50
- Journal Title
- Angewandte Chemie International Edition
- Volume
- 61
- Number
- 50
- URI
- https://scholarworks.bwise.kr/sch/handle/2021.sw.sch/21848
- DOI
- 10.1002/anie.202214342
- ISSN
- 1433-7851
1521-3773
- Abstract
- B-III subporphyrins are the legitimate ring-contracted porphyrins consisting of three pyrroles and three meso-carbons and their chemistry has been extensively developed since the first synthesis in 2006. However, subporphyrin free bases have never been synthesized, despite tremendous attempts to remove the B-III ion. Here we report that Suzuki-Miyaura coupling between alpha,alpha '-diborylated tripyrrane 1 and tetrabromide 5 gave subporphyrin free bases 6, 6 A, and free base dimer 7 in 6 %, 4 %, and 2 % yields as the first examples. Subporphyrin free bases exhibit curved bowl-like structures and distinct 14 pi-aromaticity. Steady-state and time-resolved spectroscopy revealed that the excited-state behaviors of the subporphyrin free bases are comparable with those of the corresponding B-III subporphyrins. Rotational relaxation processes in the excited states have been revealed, which enhance the electronic interactions with the meso-aryl substituents and between the two subporphyrins.
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