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Photochemical synthesis and electronic spectra of fulminene ([6]phenacene)

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Abstract

Facile synthesis of fulminene ([6]phenacene) was achieved through the Mallory reaction of 1-(1-naphthyl)-2-(1-phenanthryl)ethene or the 9-fluorenone-sensitized photo-ring-closure of 1-(1-naphthyl)-2-(1-phenanthryl)ethane. The electronic spectral properties of fulminene were investigated for the first time using photoluminescence as well as transient absorption spectroscopy. The spectral features were compared with those of a series of lower phenacene homologs such as phenanthrene ([3]phenacene), chrysene ([4]phenacene), and picene ([5]phenacene). For the [n]phenacene series, both the fluorescence and phosphorescence bands linearly red-shifted with an increase in the number of the benzene rings (n). Trends in the energy levels of the excited singlet (E S) and the triplet (E T) states were expressed as E s = −2.6n + 89.1 (kcal mol−1) and E T = −1.8n + 66.2 (kcal mol−1), respectively. In the case of fulminene, laser flash photolysis displayed a transient spectrum with an absorption maximum (λ T–Tmax ) at 675 nm, which was assigned as the triplet fulminene excited state. The λ T–Tmax values for the [n]phenacene series showed a linear correlation as a function of the ring number n, given by an equation, λ T–Tmax  = 60n + 318 (nm).

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Acknowledgments

Financial support through Grants-in-Aid for Scientific Research (KAKENHI) from JSPS (no. 23350059 to M.Y.), the Adaptable and Seamless Technology Transfer Program (A-STEP), FS Stage, Exploratory Study from JST (AS231Z01256D to H.O.) and the“Element Innovation” Project by the Ministry of Education, Culture, Sports, Science, and Technology, Japan (to M.Y.) are gratefully acknowledged. The authors thank the SC-NMR Laboratory of Okayama University for the NMR spectral measurements.

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Authors and Affiliations

  1. Division of Chemistry and Biochemistry, Graduate School of Natural Science and Technology, Okayama University, Tsushima-Naka 3-1-1, Okayama, 700-8350, Japan

    Hideki Okamoto & Kyosuke Satake

  2. Department of Chemistry and Chemical Biology, Graduate School of Engineering, Gunma University, Kiryu, Gunma, 376-8515, Japan

    Minoru Yamaji

  3. Material Science Research Group, NARD Institute, Ltd., Nishinagasu-cho 2-6-1, Amagasaki, Hyogo, 660-0805, Japan

    Shin Gohda, Kaori Sato & Hisako Sugino

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  1. Hideki Okamoto
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  2. Minoru Yamaji
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Correspondence to Hideki Okamoto or Minoru Yamaji.

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This article is dedicated to Professor Kazuhiko Mizuno in memory of his retirement.

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Okamoto, H., Yamaji, M., Gohda, S. et al. Photochemical synthesis and electronic spectra of fulminene ([6]phenacene). Res Chem Intermed 39, 147–159 (2013). https://doi.org/10.1007/s11164-012-0639-1

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  • DOI: https://doi.org/10.1007/s11164-012-0639-1

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