Tetrabromo[36]octaphyrin: A Promising Precursor of Directly Fused Porphyrin(2.1.1.1) Dimer and meso-α Fused N-Confused Porphyrin Dimer

Akito Nakai, Jinseok Kim, Takayuki Tanaka, Dongho Kim, Atsuhiro Osuka

Research output: Contribution to journalArticlepeer-review

Abstract

3,7,23,27-Tetrabromo[36]octaphyrin 2 was synthesized as a novel octaphyrin bearing two meso-free positions. Surprisingly, its ZnII and NiII complexation reactions produced a directly fused porphyrin(2.1.1.1) dimer 6, and a meso-α fused N-confused porphyrin (NCP) dimer 7, as the first example of NCP tape, respectively, via transannular C−C bond formation. While 6 exhibits a diatropic ring-current effect owing to the global 36π Möbius aromaticity, 7 shows a paratropic ring-current effect due to the global Hückel 36π antiaromaticity. In addition, the oxidation of 7 with PbO2 allowed for formation of its two-electron oxidized species 9 that exhibited a diatropic ring-current effect due to the global Hückel 34π aromaticity. This work has demonstrated that meso-free large expanded porphyrins can be a promising platform to produce novel fused porphyrinoids.

Original languageEnglish
Pages (from-to)26540-26544
Number of pages5
JournalAngewandte Chemie - International Edition
Volume60
Issue number51
DOIs
Publication statusPublished - 2021 Dec 13

Bibliographical note

Funding Information:
The work at Kyoto was supported by JSPS KAKENHI grant numbers JP18H03910, JP20K05463, and JP21H05480. A.N. appreciates a JSPS Research Fellowship for Young Scientists: 20J20954. The work at Yonsei University was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (No. 2021R1A2C300630811). The authors thank Prof. Dr. Hiromitsu Maeda and Mr. Hiroki Tanaka at Ritsumeikan University for MALDI TOF-MS measurements and Prof. Dr. Hideki Yorimitsu at Kyoto University for HR-MS measurements.

Funding Information:
The work at Kyoto was supported by JSPS KAKENHI grant numbers JP18H03910, JP20K05463, and JP21H05480. A.N. appreciates a JSPS Research Fellowship for Young Scientists: 20J20954. The work at Yonsei University was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (No. 2021R1A2C300630811). The authors thank Prof. Dr. Hiromitsu Maeda and Mr. Hiroki Tanaka at Ritsumeikan University for MALDI TOF‐MS measurements and Prof. Dr. Hideki Yorimitsu at Kyoto University for HR‐MS measurements.

Publisher Copyright:
© 2021 Wiley-VCH GmbH

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

Fingerprint

Dive into the research topics of 'Tetrabromo[36]octaphyrin: A Promising Precursor of Directly Fused Porphyrin(2.1.1.1) Dimer and meso-α Fused N-Confused Porphyrin Dimer'. Together they form a unique fingerprint.

Cite this