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Published on: June 10, 2021
Heptagon/Octagon-Fused Diporphyrins or Spiro-Pentagon-Bridged Dichlorin from p-Terphenylene-Bridged Diporphyrin
Peng Lin1, Shugang Xiong1, Yutao Rao1
1Key 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.
Abstract:
Intramolecular fusion reactions of a p-terphenylene-bridged NiII porphyrin dimer gave different products, depending upon reaction conditions. Oxidation with Fe(OTf)3 provided syn- and anti-doubly heptagon-fused NiII porphyrin dimers showing enlarged π-electronic networks, probably via a radical mechanism, while treatment with methanesulfonic acid provided a spiro-pentagon-bridged NiII chlorin dimer via acid-catalyzed Friedel-Crafts type cyclization. Further, a doubly octagon-fused NiII porphyrin dimer was synthesized via a sequence of double meso-formylation, reduction to corresponding diol, and BF3 -catalyzed cyclization.
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