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Systematic investigations on fused π-system compounds of seven benzene rings prepared by photocyclization of diphenanthrylethenes

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Abstract

We studied the photoproducts of 1-( n -phenanthryl)-2-( m -phenanthryl)ethenes ( n E m; n, m = 1, 3 and 9) for understanding photocyclization patterns based on NMR spectroscopy. The crystal structures of the photoproducts were analyzed by X-ray crystallography, and the photophysical features of the photocyclized molecules were investigated based on emission and transient absorption measurements. Phenanthrene derivatives substituted at the 1- and 3-positions were prepared for synthesizing n E m by photocyclization of stilbene derivatives. We obtained four types of primary photoproducts ( n @ m ) from the corresponding n E m. Two of them were found to have racemic molecular structures in the single crystal determined by X-ray crystallography. Besides the primary photoproducts, two types of secondary photoproducts ( n @ m PP) were isolated. Fluorescence quantum yields and lifetimes of the obtained photoproducts were determined in solution whereas the definite fluorescence quantum yields were obtained in the powder. Observation of the triplet–triplet absorption spectra in solution by laser photolysis techniques showed that intersystem crossing to the triplet state competes with the fluorescence process.

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Authors and Affiliations

  1. Education Program of Materials and Bioscience, Graduate School of Science and Engineering, Gunma University, Kiryu, Gunma, 376-8515, Japan

    Shota Fujino

  2. Division of Molecular Science, Graduate School of Science and Engineering, Gunma University, Kiryu, Gunma, 376-8515, Japan

    Minoru Yamaji

  3. Division of Earth, Life, and Molecular Sciences, Graduate School of Natural Sciences and Technology, Okayama University, Okayama, 700-8530, Japan

    Hideki Okamoto

  4. Department of Materials and Environmental Science, Institute of Industrial Science, the University of Tokyo, Meguro, Tokyo, 153-8505, Japan

    Toshiki Mutai, Isao Yoshikawa & Hirohiko Houjou

  5. Institute for Materials Chemistry and Engineering, Kyushu University, Fukuoka, 819-0395, Japan

    Fumito Tani

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  1. Shota Fujino
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  2. Minoru Yamaji
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Correspondence to Minoru Yamaji.

Additional information

Electronic supplementary information (ESI) available: The precise synthesis procedures and analytical data, X-ray crystallographic data, decay profiles of fluorescence, results of DFT calculation including tables of atom coordinates for the optimized geometries, and1H and13C NMR spectra for the compounds used in this work. CCDC 1521684-1521686. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7pp00040e

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Fujino, S., Yamaji, M., Okamoto, H. et al. Systematic investigations on fused π-system compounds of seven benzene rings prepared by photocyclization of diphenanthrylethenes. Photochem Photobiol Sci 16, 925–934 (2017). https://doi.org/10.1039/c7pp00040e

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