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New Strategy for Control of Electron Transfer in Photosynthetic Models -Local Electric Field and Hydrogen Bond

Research Project

Project/Area Number 07454249
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

OSUKA Atsuhiro  Graduate School of Science, Kyoto University Professor., 大学院・理学研究科, 教授 (80127886)

Project Period (FY) 1995 – 1996
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1996: ¥1,000,000 (Direct Cost: ¥1,000,000)
KeywordsPorphyrin / Photosynthetic Reaction Center / Electron Transfer / Electric Field Effect / Hydrogen Bond
Research Abstract

1) Porphyrin (H) -pyromellitimide (I) dyads bearing a quaternary ammonium site have been prepared and their intramolecular electron transfer reaction has been studied by measuring their fluorescence spectra in a wide range of solvents. The charges site enhances the electron transfer, but its effects are relatively small in polar solvents such as DMF and THF but are very large in low polarity media such as benzene and hexane. Pico-second time resolved transient absorption spectra revealed the formation of a charge separated state, H+-I-, giving firm evidence of the electron transfer for the fluorescence quenching. Introduction of a charges site into a more elaborated photosynthetic models such as dimer-monomer-pyromellitimide triad has been achieved through multi-step synthesis. The electron transfer dynamics of these models are now in being pursued.
2) A porphyrin host bearing 2,6-diacylaminopyridine binding site was prepared and was found to be complexed with naphthalene-diimide guest in nonpolar solvents. In benzene, the association constant is ca.10^3M.Intracomplex electron transfer has been studied by the picosecond time-resolved fluorescence lifetime and the transient absorption spectra. Electron transfer over hydrogen-bond is found to be quite effective, comparable to that of covalently-linked models having the same energy gap, but the ion-pair state was found to be rather short-lived in comparison to that in the covalently linked counterpart.

Report

(3 results)
  • 1996 Annual Research Report   Final Research Report Summary
  • 1995 Annual Research Report
  • Research Products

    (24 results)

All Other

All Publications (24 results)

  • [Publications] 大須賀篤弘: "Synthesis and Intramolecular Electron and Energy Transfer of Polyyne-and Polyene-Bridget Diporphyins" J. Org. Chem.60. 7177-7185 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 大須賀篤弘: "A Seguential Electron-Transfer Relay in Diporphyin-Porphyrin-Pyromellr timide Triads" Angew. Chem., Int. Ed. Engli. 35. 92-95 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 大須賀篤弘: "Synthesis of 1,4-Phenylene-Bridged Linear Porphyrin Arrays" J. Chem. Soc., Perkin 2. 1996. 199-203 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 大須賀篤弘: "A Stepwisr Electron-Transfer Relay Mimicking the Primary Charge Separation in Bacterial Photosynthetic Reaction Center" J. Am. Chem. Soc. 118. 155-168 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 大須賀篤弘: "Covalently Linked Pyrophesphorbide Dimers as Models of the Spectal Pain in the Photosynthetic Reaction Center" Tetrahedron. 52. 4311-4326 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 大須賀篤弘: "Meso-meso Linked Proghyrin Arrays" Angew. Chem., Int. Ed. Engli.36. 135-137 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] A.Osuka et al.: "Synthesis and Intramolecular Electron and Energy Transfers of Polyyne- and Polyene-Bridged Diporphyrins." J.Ovg.Chem.60. 7177-7185 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] A.Osuka et al.: "A Sequential Electron-Transfer Relay in Diporphyrin-Porphyrin-Pyromellitimide Triads Analogous to That in the Photosynthetic Reaction Center." Angew.Chem., Int.Ed.Enpl. 35. 92-95 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] A.Osuka et al.: "Synthesis of 1,4-Phenylene-Bridged Linear Porphyrin Arrays." J.Chem Soc.Perkin 2. 1996. 199-203 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] A.Osuka et al.: "A Stepwise Electron-Transfer Relay Mimicking the Primary Charge Separation in Bacterial Photosynthetic Reaction Center." J.Am.Chem.Soc.118. 155-168 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] A.Osuka et al.: "Covalently Linked Pyropheophorbide Dimers as Models of the Special Pair in the Photosynthetic Reaction Center." Tetrahedron. 52. 4311-4326 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] A.Osuka et al.: "Meso-meso Linked Porphyrin Arrays." Angew.Chem., Int.Ed.Enpl. 36. 135-139 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 大須賀篤弘: "Covalently Linked Pyropheophorbide Dimers as Models of the Special pair in the photosynthetic Reaction Center" Tetrahedron. 52・12. 4311-4326 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 篠田哲史: "Transesterification of the 2-Keto Ester in Methiyl Pheophorbide-a" Tetrahedron Letters. 37・28. 4945-4948 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 大須賀篤弘: "Mimicking Charge Separahon of the Bacterial photosynthetic Reaction Center with Porphyrin Arrays" Spectrum. 9・3. 11-13 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 大須賀篤弘: "Meso-meso linked Porphyrin Arrays" Angen Chem.,Int.Ed.Englih. (印刷中).

    • Related Report
      1996 Annual Research Report
  • [Publications] 川端繁樹: "Singlet Energy Transfer in Bis(phenyle thyil)phemylene-bridyed Zie-Free bose Hybrid Diporphyrins" J.chem.Soc.,Perkir Trans 2. (印刷中).

    • Related Report
      1996 Annual Research Report
  • [Publications] 大須賀篤弘: "Synthesis of a Covalently Linked Bacteriopyropheopherbide-pyrphespherbide Hyblid Dimer" Heterocycles. 44・1. 165-168 (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] 大須賀 篤弘: "Change Separation in 2inc-Diporphyrin-2inc Porphyrin-Pyromellinimide Quinone Tietrads" Chemistry Letters. 1995. 591-592 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 大須賀 篤弘: "Synthesis of Partially Metalated, Conformationally Restricted Oligomeric Porphyrius for Study Photosynthetic change Jeparation" Tetrakedron Letters. 36. 5781-5784 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 大須賀 篤弘: "Intracomplex Election Transfer in a Hydrogen-Bonded Porphyrin-Diimide System" Chemistry Letters. 1995. 913-914 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 大須賀 篤弘: "Synthesis and Intramelecular Electron- and Energy-Tranfer Reactions of Polyyne or Polyene-bridged Diporphyrins" Journal of Organic Chemistry. 60. 7177-7185 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 大須賀 篤弘: "A Sequential Electron-Transfer Relay in Dipurphyin-Porphyin-Pyremellitimide Triads Analogous to that in the Photosynthetic Reaction Center" Angewanate Chenie, Iuternational Edition, English. 35. 92-95 (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] 大須賀 篤弘: "A Stepwise Electron-Transfer Relay Mimicking the Primary Change Jeparation in Bacterial Photosynthetic Reaction Center" Journal of the American Chemical Society. 118. 155-168 (1996)

    • Related Report
      1995 Annual Research Report

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Published: 1996-04-01   Modified: 2016-04-21  

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