Synthesis and Properties of Hybrid Porphyrin Tapes

Authors

  • Takayuki Tanaka,

    1. Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3970
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  • Byung Sun Lee,

    1. Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul 120-749 (Korea)
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  • Dr. Naoki Aratani,

    1. Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3970
    2. PRESTO (Japan) Science and Technology Agency
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  • Dr. Min-Chul Yoon,

    1. Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul 120-749 (Korea)
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  • Prof. Dr. Dongho Kim,

    Corresponding author
    1. Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul 120-749 (Korea)
    • Spectroscopy Laboratory for Functional π-Electronic Systems and Department of Chemistry, Yonsei University, Seoul 120-749 (Korea)
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  • Prof. Dr. Atsuhiro Osuka

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

Hybrid porphyrin tapes 3 and 4, consisting of a mixture of 3,5-di-tert-butylphenyl-substituted donor-type ZnII–porphyrins and pentafluorophenyl-substituted acceptor-type ZnII–porphyrins, were prepared by a synthetic route involving cross-condensation reaction of a NiII–porphyrinyldipyrromethane and pentafluorophenyldipyrromethane with pentafluorobenzaldehyde followed by appropriate demetalation, remetalation, and oxidative ring-closure reaction. The NiII-substituted porphyrin tapes 5 (Ni-Zn-Ni) and 6 (Ni-H2-Ni) were also prepared through similar routes. The hybrid porphyrin tapes 3 and 4 are more soluble and more stable than normal porphyrin tapes 1 and 2 consisting of only donor-type ZnII–porphyrins. The solid-state and crystal packing structures of 3, 4, and 5 were elucidated by single-crystal X-ray diffraction analysis. Singly mesomeso-linked hybrid porphyrin arrays 12 and 14 exhibit redox potentials that roughly correspond to each constituent porphyrin segments, while the redox potentials of the hybrid porphyrin tapes 3 and 4 are positively shifted as a whole. The two-photon absorption (TPA) values of 1–6 were measured by using a wavelength-scanning open aperture Z-scan method and found to be 1900, 21 000, 2200, 27 000, 24 000, and 26 000 GM, respectively. These results illustrate an important effect of elongation of π-electron conjugation for the enhancement of TPA values. The hybrid porphyrin tapes show slightly larger TPA values than the parent ones.

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