Metal-Mediated Synthesis of Antiaromatic Porphyrinoids from a BODIPY Precursor

Authors

  • Takafumi Sakida,

    1. Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Nagoya 464-8603 (Japan), Fax: (+81) 52-789-5113
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  • Shigeru Yamaguchi,

    1. Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Nagoya 464-8603 (Japan), Fax: (+81) 52-789-5113
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  • Prof. Dr. Hiroshi Shinokubo

    Corresponding author
    1. Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Nagoya 464-8603 (Japan), Fax: (+81) 52-789-5113
    • Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Nagoya 464-8603 (Japan), Fax: (+81) 52-789-5113
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  • We are indebted to Prof. Kazuyuki Tatsumi and Prof. Yasuhiro Ohki (Nagoya University) for help with X-ray analysis and Prof. Atsuhiro Osuka and Prof. Naoki Aratani (Kyoto University) for help with NIR fluorescence measurements. This work was supported by MEXT (Japan) Grants-in-Aid for Scientific Research (Nos. 21685011 and 21108510 “pi-Space”) and the Global COE Program in Chemistry of Nagoya University. H.S. also acknowledges the Asahi Glass Foundation for financial support. S.Y. appreciates the JSPS Research Fellowships for Young Scientists. BODIPY=boron dipyrrin.

Abstract

original image

Metallic route to antiaromaticity: The synthesis of a butadiyne-bridged cyclic BODIPY dimer (see structure; C white, B orange, N blue, F green) and trimer was achieved through Pd-catalyzed Stille coupling and Cu-mediated Glaser-type coupling. These cyclic BODIPYs were found to be stable 24π- and 36π-antiaromatic porphyrinoids with planar conformations, and their structures, electronic states, and reactivity were explored.

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