Deprotonation-Induced Aromaticity Enhancement and New Conjugated Networks in meso-Hexakis(pentafluorophenyl)[26]hexaphyrin

Authors

  • Won-Young Cha,

    1. Department of Chemistry and Spectroscopy Laboratory for Functional π-Electronics System, Yonsei University 262 Seongsanno, Seodaemun-gu, Seoul 120-749 (Korea), Fax: (+81) 2-2123-2434
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  • Jong Min Lim,

    1. Department of Chemistry and Spectroscopy Laboratory for Functional π-Electronics System, Yonsei University 262 Seongsanno, Seodaemun-gu, Seoul 120-749 (Korea), Fax: (+81) 2-2123-2434
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  • Dr. Min-Chul Yoon,

    1. Department of Chemistry and Spectroscopy Laboratory for Functional π-Electronics System, Yonsei University 262 Seongsanno, Seodaemun-gu, Seoul 120-749 (Korea), Fax: (+81) 2-2123-2434
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  • Young Mo Sung,

    1. Department of Chemistry and Spectroscopy Laboratory for Functional π-Electronics System, Yonsei University 262 Seongsanno, Seodaemun-gu, Seoul 120-749 (Korea), Fax: (+81) 2-2123-2434
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  • Byung Sun Lee,

    1. Department of Chemistry and Spectroscopy Laboratory for Functional π-Electronics System, Yonsei University 262 Seongsanno, Seodaemun-gu, Seoul 120-749 (Korea), Fax: (+81) 2-2123-2434
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  • Sho Katsumata,

    1. Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka 819-0395 (Japan), Fax: (+81) 92-802-2867
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  • Masaaki Suzuki,

    1. Department of Chemistry, Graduated School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3970
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  • Hirotaka Mori,

    1. Department of Chemistry, Graduated School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3970
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  • Prof. Dr. Yoshiya Ikawa,

    Corresponding author
    1. Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka 819-0395 (Japan), Fax: (+81) 92-802-2867
    • Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka 819-0395 (Japan), Fax: (+81) 92-802-2867
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  • Prof. Dr. Hiroyuki Furuta,

    Corresponding author
    1. Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka 819-0395 (Japan), Fax: (+81) 92-802-2867
    • Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka 819-0395 (Japan), Fax: (+81) 92-802-2867
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  • Prof. Dr. Atsuhiro Osuka,

    Corresponding author
    1. Department of Chemistry, Graduated School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3970
    • Department of Chemistry, Graduated School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3970
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  • Prof. Dr. Dongho Kim

    Corresponding author
    1. Department of Chemistry and Spectroscopy Laboratory for Functional π-Electronics System, Yonsei University 262 Seongsanno, Seodaemun-gu, Seoul 120-749 (Korea), Fax: (+81) 2-2123-2434
    • Department of Chemistry and Spectroscopy Laboratory for Functional π-Electronics System, Yonsei University 262 Seongsanno, Seodaemun-gu, Seoul 120-749 (Korea), Fax: (+81) 2-2123-2434
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Abstract

meso-Hexakis(pentafluorophenyl)-substituted neutral hexaphyrin with a 26π-electronic circuit can be regarded as a real homolog of porphyrin with an 18π-electronic circuit with respect to a quite flat molecular structure and strong aromaticity. We have investigated additional aromaticity enhancement of meso-hexakis(pentafluorophenyl)[26]hexaphyrin(1.1.1.1.1.1) by deprotonation of the inner N[BOND]H groups in the macrocyclic molecular cavity to try to induce further structural planarization. Deprotonated mono- and dianions of [26]hexaphyrin display sharp B-like bands, remarkably strong fluorescence, and long-lived singlet and triplet excited-states, which indicate enhanced aromaticity. Structural, spectroscopic, and computational studies have revealed that deprotonation induces structural deformations, which lead to a change in the main conjugated π-electronic circuit and cause enhanced aromaticity.

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