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2006 Fiscal Year Final Research Report Summary

Construction of supramolecular light-harvesting antenna and photo-induced electron transfer systems by use of coordination-organized special pair of porphyrin

Research Project

Project/Area Number 15205020
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Research Field Functional materials chemistry
Research InstitutionNara Institute of Science and Technology

Principal Investigator

KOBUKE Yoshiaki  Nara Institute of Science and Technology, Graduate School of Materials Science, Professor, 物質創成科学研究科, 教授 (80026195)

Co-Investigator(Kenkyū-buntansha) SATAKE Akiharu  Nara Institute of Science and Technology, Graduate School of Materials Science, Assistant Professor, 物質創成科学研究科, 助手 (00277831)
OGAWA Kazuya  Nara Institute of Science and Technology, Graduate School of Materials Science, Assistant Professor, 物質創成科学研究科, 助手 (50335486)
Project Period (FY) 2003 – 2006
Keywordsporphyrin / phthalocyanine / supramolecular science / artificial photosynthesis / two photon absorption / photo-dynamic therapy / molecular electronics
Research Abstract

Light-harvesting antenna, photo-induced electron transfer, photo-voltaic cell, and two-photon absorption systems by use of coordination-organized special pair of porphyrins were investigated. To construct stable macrocyclic porphyrin systems, supramolecular methodology and following metathesis linking was developed. Excited energy hopping (EEH) rates of the porphyrin macrorings were estimated as 1/(tens ps) by ultra fast time-resolved spectroscopic techniques. The much shorter EEH time constants compared with fluorescence lifetime indicate that the excited energy can be stored in the macroring for a long period. Photo-induced electron transfer of special pair having electron acceptors and/or donors was also investigated by ultra fast laser photolysis. The special pair moiety is important for acceleration of charge separation and deceleration of charge recombination due to its small reorganization energy. Photo-voltaic cell was constructed on ITO electrode modified by TiO2 and special pairs, and arylphosphonic acid moiety attached to the special pair showed good performance. A supramolecular composite of macrocyclic porphyrin ring and tripyridyl ligand were constructed as a mimic of light-harvesting complex I-reaction center composite. Instead of porphyrin, a special pair composed of two imidazolylphthalocyanines was synthesized. Split of the Q-band in absorption spectrum and charge delocalization of one-electron oxidation state were observed. Acetylene-linked porphyrins having extremely strong two-photon absorption were synthesized. These can be useful for photodynamic therapy anti-cancer agents working at deep part and 3-dimetional optical data storage.

  • Research Products

    (19 results)

All 2006 Other

All Journal Article (18 results) Patent(Industrial Property Rights) (1 results)

  • [Journal Article] Photoinduced Electron Transfer and Excitation Energy Transfer in Directly Linked Zinc Porphyrin / Zinc Phthalocyanine Composite2006

    • Author(s)
      F.Ito
    • Journal Title

      J. Phys. Chem., A 110

      Pages: 12734-12742

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Efficient Charge Injection from the S_2 Photoexcited State of Special-Pair Mimic Porphyrin Assemblies Anchored on a Titanium-Modified ITO Anode2006

    • Author(s)
      M.Morisue
    • Journal Title

      Chem. Eur. J. 12

      Pages: 8123-8135

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Single Molecular Observation of Penta- and Hexagonic Assembly of Bisporphyrin on a Gold Surface2006

    • Author(s)
      A.Satake
    • Journal Title

      Chem. Commun.

      Pages: 2542-2544

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Supramolecular Array of Imidazolylethynyl-zinc-porphyrin2006

    • Author(s)
      A.Satake
    • Journal Title

      J. Organomet. Chem. 692

      Pages: 635-644

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Substituent Effect on Two-photon Absorption Properties of Conjugated Porphyrins2006

    • Author(s)
      K.Ogawa
    • Journal Title

      J. Porphyrins & Phthalocynines

      Pages: 735-744

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Assemblies of Supramolecular Porphyrin Dimers in Pentagonal and Hexagonal Arrays Exhibiting Light-Harvesting Antenna Function2006

    • Author(s)
      F.Hajjaj
    • Journal Title

      J. Am. Chem. Soc. 128

      Pages: 4612-4623

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] A Supramolecular Photosynthetic Triad of Slipped Cofacial Porphyrin Dimer, Ferrocene, and Fullerene2006

    • Author(s)
      H.Nakagawa
    • Journal Title

      Chem. Commun.

      Pages: 1560-1562

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Water-soluble Bis(imidazolylporphyrin) Self-assemblies with Large Two-photon Absorption Cross Sections as Agents for Photodynamic Therapy2006

    • Author(s)
      K.Ogawa
    • Journal Title

      J. Med. Chem. 49

      Pages: 2276-2283

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Photoinduced Electron Transfer and Excitation Energy Transfer in Directly Linked Zinc Porphyrin / Zinc Phthalocyanine Composite.2006

    • Author(s)
      F.Ito, Y.Ishibashi, S.R.Khan, H.Miyasaka, K.Kameyama, M.Morisue, A.Satake, K.Ogawa, Y.Kobuke
    • Journal Title

      J. Phys. Chem., A 110

      Pages: 12734-12742

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Efficient Charge Injection from the S_2 Photoexcited State of Special-Pair Mimic Porphyrin Assemblies Anchored on a Titanium-Modified ITO Anode.2006

    • Author(s)
      M.Morisue, N.Haruta, D.Kalita, Y.Kobuke
    • Journal Title

      Chem. Eur. J. 12

      Pages: 8123-8135

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Single Molecular Observation of Penta-and Hexagonic Assembly of Bisporphyrin on a Gold Surface.2006

    • Author(s)
      A.Satake, H.Tanaka, F.Hajjaj, T.Kawai, Y.Kobuke
    • Journal Title

      Chem. Commun.

      Pages: 2542-2544

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Supramolecular Array of Imidazolylethynyl-zinc-porphyrin.2006

    • Author(s)
      A.Satake, O.Shoji, Y.Kobuke
    • Journal Title

      J. Organomet. Chem. 692

      Pages: 635-644

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Substituent Effect on Two-photon Absorption Properties of Conjugated Porphyrins.2006

    • Author(s)
      K.Ogawa, J.Dy, Y.Kobuke
    • Journal Title

      J. Porphyrins & Phthalocynines

      Pages: 735-744

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Assemblies of Supramolecular Porphyrin Dimers in Pentagonal and Hexagonal Arrays Exhibiting Light-Harvesting Antenna Function.2006

    • Author(s)
      F.Hajjaj, Z.S.Yoon, M.-C.Yoon, J.Park, A.Satake, D.Kim, Y.Kobuke
    • Journal Title

      J. Am. Chem. Soc. 128

      Pages: 4612-4623

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] A Supramolecular Photosynthetic Triad of Slipped Cofacial Porphyrin Dimer, Ferrocene, and Fullerene.2006

    • Author(s)
      H.Nakagawa, K.Ogawa, A.Satake, Y.Kobuke
    • Journal Title

      Chem. Commun.

      Pages: 1560-1562

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Water-soluble Bis (imidazolylporphyrin) Self-assemblies with Large Two-photon Absorption Cross Sections as Agents for Photodynamic Therapy.2006

    • Author(s)
      K.Ogawa, H.Hasegawa, Y.Inaba, Y.Kobuke, H.Inouye, Y.Kanemitsu, E.Kohno, T.Hirano, S.Ogura, I.Okura
    • Journal Title

      J. Med. Chem. 49

      Pages: 2276-2283

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Fine-Tuning of a Ferrocene/Porphyrin/ITO Redox Cascade for Efficient Sequential Electron Transfer Commenced by an S_2 Photoexcited Special-Pair Mimic

    • Author(s)
      M.Morisue
    • Journal Title

      Chem. Commun. (印刷中)

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Fine-Tuning of a Ferrocene/Porphyrin/ITO Redox Cascade for Efficient Sequential Electron Transfer Commenced by an S_2 Photoexcited Special-Pair Mimic.

    • Author(s)
      M.Morisue, D.Kalita, N.Haruta, Y.Kobuke
    • Journal Title

      Chem. Commun. (in press)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Patent(Industrial Property Rights)] 色素会合体を形成する色素、色素会合体を含有する組成物、および色素会合体の構造変換を用いた情報記録再生方法2006

    • Inventor(s)
      小夫家芳明, 佐竹彰治
    • Industrial Property Rights Holder
      奈良先端科学技術大学院大学
    • Industrial Property Number
      特許権、特願2006-181847
    • Filing Date
      2006-06-30
    • Description
      「研究成果報告書概要(和文)」より

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Published: 2008-05-27  

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