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Construction of 3D structure of porphyrin polymer complexes and control of their electronic transition

Research Project

Project/Area Number 11650903
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field 高分子合成
Research InstitutionThe University of Tokyo

Principal Investigator

SEGAWA Hiroshi  The University of Tokyo, Graduate School of Arts and Sciences, Associate Professor, 大学院・総合文化研究科, 助教授 (50216511)

Project Period (FY) 1999 – 2001
Project Status Completed (Fiscal Year 2001)
Budget Amount *help
¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 2001: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 2000: ¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 1999: ¥1,500,000 (Direct Cost: ¥1,500,000)
Keywordsporphyrin / polymer compley / elecfron transfer / Tc-radical / triplet state / photpinduced electron transfer / cheinical oxidation / photo-oxidation / 電子遷移 / 元誘起電子移動 / 励起エネルギー移動 / 分子アーキテクチャー
Research Abstract

The electronic transition of 3D porphyrin arrays are important not only for elucidation of the functions of the natural systems but also for application of the functions to molecular architecture. In this study, a novel systematic synthesis of various types of porphyrin arrays were investigated.
Among them, the excited state properties of phosphorus(V) porphyrin dimers were investigated on the contribution of a charge transfer (CT) state. The lifetime of the symmetry-disturbed "center-to-edge" dimer was remarkably shortened through the CT state. The photo-induced Electron Transfer through the CT state was observed in the triad molecular systems of the phosphorus(V) porphyrins. On the other hand, zinc meso-(1-pyrenyl)triphenylporphyrin derivatives were synthesized and investigated on their photophysical properties. While the S1 fluorescence of the porphyrin derivatives was not quenched by the pyrenyl group at all, the S2 fluorescence was remarkably quenched through intramolecular CT state.
On the other hand, poly-π-radical cations of directly meso-linked Zn(II)porphyrin arrays (dimer ZnP2, trimer ZnP3, and tetramer ZnP4) were synthesized and investigated for spin alignment. The high-spin states based on the exchange interaction between adjacent porphyrin π-radicals were observed. The temperature dependence indicated a temperature-dependent singlet-triplet crossover at the relatively high temperature.

Report

(4 results)
  • 2001 Annual Research Report   Final Research Report Summary
  • 2000 Annual Research Report
  • 1999 Annual Research Report
  • Research Products

    (13 results)

All Other

All Publications (13 results)

  • [Publications] Feipeng Wu, H.Segawa: "High Yield Squthesis Route for Directly meso-Liuked porpugrin Dimers and Their Properties"Photographic Science and Photochemistry. 17. 316-322 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Feipeng Wu, H.Segawa: "Construction of meso-Linked Porphyrin Polycuers via Electrochernical Oxidative Coupling"Acta Chimica Shimica. 58. 122-126 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Feipeng Wu, Yasuhiro Maeda, K.Hirakawa, H.Segawa: "Electrochemical Construction of Organized Porplyrin Polymers toward Nano-Molecular Spin System"Hyper Structured Molecules III. 124-135 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] H.Segawa, D.Machida, K.Hirakawa, Y.Senshu, J.Nakazaki, Feipeng Wu: "Spin Alignment of Orthogonal π-Radicals of Directly meso-Linked Porphyrin Arrays"Chem Commun. 3032-3033 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Feipeng Wu, H. Segawa: "High Yield Synthesis Route for Directly meso-Linked Porphyrin Dimers and Their Properties"Photographic Science and Photochemistry. 17. 316-322 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Feipeng Wu, H. Segawa: "Construction of meso- Linked Porphyrin Polymers via Electrochemical Oxidative Coupling"Acta Chimica Shinica. 58. 122-126 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Feipeng Wu, Y. Maeda, K. Hirakawa, H. Segawa: "Electrochemical Construction of Organized Porphynn Polymers toward Nano-Molecular Spin Systems"Hyper Structured Molecules III. 124-135 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] H. Segawa, D. Machida, Y. Sensyu, J Nakazaki, K. Hirakawa, Feipeng Wu: "Spin Alignment of Orthogonal π-Radicals of Directly meso- Linked Porphyrin Arrays"Chem. Commun. 3032-3033 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Feipeng Wu: "Electrochemical Constraction of Organized Porphyrin Polymers toward Nano-Mdecular Spin Systems"Hyper Structured Molecules III. 124-135 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Feipeng Wu: "High Yield Synthesis Route for Directly meso-Linked Porphyrin Dimers"Photographic Science and Photochemistry. 17. 316-322 (1999)

    • Related Report
      2000 Annual Research Report
  • [Publications] Feipeng Wu: "Construction of meso-Linked Prophyrin Polymers via Electrochemical Oxidative Coupling"Acta Chimica Shinica. 58. 122-126 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Hiroshi Segawa et al.: "Excitation energy transfer and photo-induced election transfer in axial bispyrenyl phosphcrus (V) porphyrin derivatives"J. Photochem. Photobiol., A, Chemistry. 123. 67-76 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Hiroshi Segawa et al.: "Syuthesis and photophysical properties of "center-to-edge" type P(V) porphyrin arrays"J. Chem. Soc., Perkin Trans 2,. 1521-1529 (1999)

    • Related Report
      1999 Annual Research Report

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Published: 1999-04-01   Modified: 2016-04-21  

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