Heptagon/Octagon-Fused Diporphyrins or Spiro-Pentagon-Bridged Dichlorin from p-Terphenylene-Bridged Diporphyrin

Peng Lin; Shugang Xiong; Yutao Rao; Ling Xu; Mingbo Zhou; Bangshao Yin; Atsuhiro Osuka; Jianxin Song

doi:10.1002/asia.202300018

Heptagon/Octagon-Fused Diporphyrins or Spiro-Pentagon-Bridged Dichlorin from p-Terphenylene-Bridged Diporphyrin

Chem Asian J. 2023 Mar 14;18(6):e202300018. doi: 10.1002/asia.202300018. Epub 2023 Feb 13.

Authors

Peng Lin¹, Shugang Xiong¹, Yutao Rao¹, Ling Xu¹, Mingbo Zhou¹, Bangshao Yin¹, Atsuhiro Osuka¹, Jianxin Song¹

Affiliation

¹ Key Laboratory of Chemical Biology and Traditional Chinese Medicine, Ministry of Education of China, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, 410081, P. R. China.

PMID: 36725682
DOI: 10.1002/asia.202300018

Abstract

Intramolecular fusion reactions of a p-terphenylene-bridged Ni^II porphyrin dimer gave different products, depending upon reaction conditions. Oxidation with Fe(OTf)₃ provided syn- and anti-doubly heptagon-fused Ni^II porphyrin dimers showing enlarged π-electronic networks, probably via a radical mechanism, while treatment with methanesulfonic acid provided a spiro-pentagon-bridged Ni^II chlorin dimer via acid-catalyzed Friedel-Crafts type cyclization. Further, a doubly octagon-fused Ni^II porphyrin dimer was synthesized via a sequence of double meso-formylation, reduction to corresponding diol, and BF₃ -catalyzed cyclization.

Keywords: antiaromaticity; chlorin; fusion; near infrared absorption; porphyrin dimer.

Abstract

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