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Photochemical Epoxidation with Water as Electron and Oxygen Source upon Visible Light Irradiation

Research Project

Project/Area Number 11555231
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section展開研究
Research Field 工業物理化学
Research InstitutionTOKYO METROPOLITAN UNIVERSITY

Principal Investigator

INOUE Haruo  Tokyo Metropolitan University, Graduate Course of Engineering, Professor, 大学院・工学研究科, 教授 (90087304)

Co-Investigator(Kenkyū-buntansha) SHIMADA Tetsuya  Tokyo Metropolitan University, Graduate Course of Engineering, Research Associate, 大学院・工学研究科, 助手 (50252317)
TACHIBANA Hiroshi  Tokyo Metropolitan University, Graduate Course of Engineering, Assistant Professor, 大学院・工学研究科, 講師 (00163478)
SGIRAGAMI Tsutomu  Miyazaki University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (60235744)
EHARA Shunji  Dainippon Ink and Chemicals, Inc. Epoxy Compounds Technical Department, General Manager, エポキシ技術クリレープ部長, 部長
TAKAGI Shinsuke  Tokyo Metropolitan University, Graduate Course of Engineering, Research Associate, 大学院・工学研究科, 助手 (40281240)
Project Period (FY) 1999 – 2001
Project Status Completed (Fiscal Year 2001)
Budget Amount *help
¥13,700,000 (Direct Cost: ¥13,700,000)
Fiscal Year 2001: ¥1,900,000 (Direct Cost: ¥1,900,000)
Fiscal Year 2000: ¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1999: ¥9,700,000 (Direct Cost: ¥9,700,000)
KeywordsPhotochemical splitting of water / Porphyrin / Epoxidation / Oxygenation / Metal complex / Artificial photosynthesis / Antimony / Ruthenium
Research Abstract

Efficient epoxidation of alkenes with water as an electron donor and oxygen atom donor sensitized by metalloporphyrin such ruthenium (II) porphyrin has been revealed to proceed upon visible light irradiation without using strong oxidizing agents in this research project The epoxidation reaction could be one of the most promising approaches to get an useful reaction which can utilize visible light. The following results have been obtained through the term of the present research.
1) Development of novel composite reaction systems for a highly efficient photochemical epoxidation reaction sensitized by ruthenium (II) porphyrin : For establishing the efficient photochemical oxygenation reactions of alkene with water as an electron and an oxygen atom donor, detailed study on construction of two independent systems 1) having an efficient absorption of visible light and a high reactivity to form the active reactive intermediate, cation radical of porphyrins, through an electron transfer from t … More he excited porphyrins to electron acceptors, and 2) cation radical of the porphyrins. Novel composite systems combining the two independent systems by a hole transfer reaction was developed.
2) Extension of substrates employed in the photochemical epoxidation : Various alkenes such as cyclic alkenes (cyclohexene, norbornene, and cyclooctene), aromatic alkenes (styrene and stilbene) and acyclic alkenes (1-hexene) were examined for the photochemical epoxidation. Among them norbornene has been revealed to exhibit a high selectivity of epoxide formation in nearly to 100 % with a high reactivity of the quantum yield of ca.0.4.
3) Development of novel anisotropic reaction fields for the photochemical electron transfer reaction : Novel anisotropic reaction fields such as layered metal oxide semiconductors as non-sacrificial electron accepting systems was adopted for the photo-redox reactions. A multi-channel glass plate with well ordered strucute where straight channel penetrating and being allined in perpendicular to the plate was also used for the anisotropic reaction fields. Less

Report

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

    (31 results)

All Other

All Publications (31 results)

  • [Publications] T.Yui, H.Yoshida, H.Tachibana, D.A.Tryk, H.Inoue: "Intercalation of Polyfluorinated Surfactants into Clay Minerals and the Characterization of the Hybrid Compounds"Langmuir. 18. 891-896 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] A.Morimoto, T.Yatsuhashi, T.Shimada, L.Biczok, D.A.Tryk, H.Inoue: "Radiationless Deactivation of an Intramolecular Chage Transfer Excited State through Hydrogen Bonding : Effect of Molecular Structure and Hard-Soft Anionic Character in the Excited State"J.Phys.Chem.A.. 105. 10488-10496 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] A.Morimoto, T.Yatsuhashi, T.Shimada, S.Kumazaki, K.Yoshihara, H.Inoue: "Molecular Mechanism of the Intermolecular Hydrogen Bond between 2-Piperidinoanthraquinone and Alcohol in the Excited State : Direct Observation of the Out-of-Plane Mode Interaction with Alcohol by Transient Absorption Studies"J.Phys.Chem.A.. 105. 8840-8849 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] M.Sugita, T.Shimada, H.Tachibana, H.Inoue: "Factors controlling the deactivation induced by hydrogen-bonding interaction : Steric and electronic effects on dual anisotropic relaxation processes"Phys.Chem.Chem.Phys.. 3. 2012-2017 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] S.Takagi, T.Shimada, T.Yui, H.Inoue: "High Density Adsorption of Porphyrins onto Clay Layer without Aggregation : Characterization of Smectite-Cationic Porphyrin Complex"Chem.Lett.. 128-129 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Y.Yamaguchi, T.Yui, S.Takagi, T.Shimada, H.Inoue: "Intercalation of Metallopophyrin-surfactant Complex into Layered Niobate and the Photochemical Injection of Electrons to Niobate"Chem.Lett.. 644-645 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T. Yui, H, Yoshida, H. Tachibana, D.A. Tryk, and H. Inoue: "Intercalation of Polyfluorinated Surfactants into Clay Minerals and the Characterization of the Hybrid Compounds"Langmuir. 18. 891-896 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] A. Morimoto, T. Yatsuhashi, T. Shimada, S. Kumazaki, K, Yoshihara, and H. Inoue: "Molecular Mechanism of the Intermolecular Hydrogen Bond between 2-Piperidinoanthraquinone and Alcohol in the Excited State : Direct Observation of the Out-of-Plane Mode Interaction with Alcohol by Transient Absorption Studies"J. Phys. Chem. A. 105. 8840-8849 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] A. Morimoto, T. Yatsuhashi, T. Shimada, L, Biczok, D. A. Tryk, and H. Inoue: "Radiationless Deactivation of an Intramolecular Chage Transfer Excited State through Hydrogen Bonding : Effect of Molecular Structure and Hard-Soft Anionic Character in the Excited State"J. Phys. Chem. A. 105. 10488-10496 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] M. Sugita, T. Shimada, H. Tachibana, and H. Inoue: "Factors controlling the deactivation induced by hydrogen-bonding interaction : Steric and electronic effects on dual anisotropic relaxation processes"Phys. Chem, Chem. Phys.. 3. 2012-2017 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] S. Takagi, T. Shimada, T. Yui, and H. Inoue: "High Density Adsorption of Porphyrins onto Clay Layer without Aggregation : Characterization of Smectite-Cationic Porphyrin Complex"Chem. Lett.. 2001. 128-129 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Y. Yamaguchi, T. Yui, S. Takagi, T. Shimada, and H. Inoue: "Intercalation of Metalloporphyrin-Surfactant Complex into Layered Niobate and the Photochemical Injection of Electrons to Niobate"Chem. Lett.. 644-645 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T.Yui, H.Yoshida, H.Tachibana, D.A.Tryk, H.Inoue: "Intercalation of Polyfluorinated Surfactants into Clay Minerals and the Characterization of the Hybrid Compounds"Langmuir. 18. 891-896 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] A.Morimoto, T.Yatsuhashi, T.Shimada, L.Biczok, D.A.Tryk, H.Inoue: "Radiationless Deactivation of an Intramolecular Chage Transfer Excited State through Hydrogen Bonding : Effect of Molecular Structure and Hard-Soft Anionic Character in the Excited State"J.Phys.Chem.A. 105. 10488-10496 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] A.Morimoto, T.Yatsuhashi, T.Shimada, S.Kumazaki, K.Yoshihara, H.Inoue: "Molecular Mechanism of the Intermolecular Hydrogen Bond between 2-Piperidinoanthraquinone and Alcohol in the Excited State : Direct Observation of the Out-of-Plane Mode Interaction with Alcohol by Transient Absorption Studies"J.Phys.Chem.A. 105. 8840-8849 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] M.Sugita, T.Shimada, H.Tachibana, H.Inoue: "Factors controlling the deactivation induced by hydrogen-bonding interaction : Steric and electronic effects on dual anisotropic relaxation processes"Phys.Chem.Chem.Phys.. 3. 2012-2017 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] S.Takagi, T.Shimada, T.Yui, H.Inoue: "High Density Adsorption of Porphyrins onto Clay Layer without Aggregation : Characterization of Smectite-Cationic Porphyrin Complex"Chem.Lett.. 128-129 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Y.Yamaguchi, T.Yui, S.Takagi, T.Shimada, H.Inoue: "Intercalation of Metalloporphyrin-Surfactant Complex into Layered Niobate and the Photochemical Injection of Electrons to Niobate"Chem.Lett.. 644-645 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] L.Biczok,T.Berces,T.Yatsuhashi,H.Tachibana,and H.Inoue,: "The Role of Intersystem Crossing in the Deactivation of the Singlet Excited Aminofluorenones."Phys.Chem.Chem Phys.,. 2. 980-985 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] S.Takagi,T.Shjimada,T.Yui,and H.Inoue,: "High Density Adsorption of Porphrins onto Clay Layer without Aggregation : Characterization of Smectite-Cationic Porphyrin Complex,"Chem.Lett.,. 128-129 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] M.Iyoda,N.Nkamura,M.Todaka,S.Ohtsu,K.Hara,Y.Kuwatani,M.Yoshida,H.Matsuyama,M.Sugita,H.Tachibana,and H.Inoue,: "Novel Synthesis of Hexaaryl [3] radialenes via Dibromo [3] dendralenes."Tetrahedron Lett.,. 41. 7059-7064 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] T.Shinoda,T.Nishiwaki,and H.Inoue,: "Decomposition of poly (4-hydroxystyrene sulfone) in Alkaline Aqueous Solution."J.Polymer Sci : A : Polymer Chem.,. 38. 2760-2766 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Y.Aikawa,T.Shimada,H.Tachibana,and H.Inoue,: "Photophysical Properties of Fluorenones with Chiral Substituents and their Asymmetric Recognition through Intermolecular Hydrogen Bonding Interactions in the Excited States."J.Photosci.,. 6. 165-170 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] R.Matsuoka,T.Yui,R.Sasai,K.Takagi,and H.Inoue,: "Enghanced Aggregation of Tin(IV)porphyrins in a Polyfluorinated Surfactant-Clay Hybrid Environment."Mol.Cryst.Liq.Cryst.,. 341. 333-338 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] S.Takagi, H.Morimoto, T.Shiragami, H.Inoue,: "Visible light induced oxygenetion of cylcohexene with activation of water sensitized by dihydroxy coordinated tetraphenylporphyrinatotin(IV)."Res. Chem. Intedrmed., 26,171-183(2000).. 26. 171-183 (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] L.Biczok, T.Berces, and H.Inoue,: "Effects of Molecular Structure and HYdrogen Bonding on the Radiationless Deactivation of Singlet Excited Fluorenone Derivatives,"J. Phys. Chem. A, 103, 3837-3842(1999).. 103. 3837-3842 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Y.Kameo, S.Takahashi, M.Krieg-Koward, T.Ohmachi, S.Takagi, and H.Inoue,: "Surface Polyfluorinated Micelles."J.Phys. Chem. B, 103, 9562-9568(1999).. 103. 9562-9568 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] H.Kusaka, M.Uno, M.Krieg-Kowald, T.Ohmachi, S.Kidokoro, T.Yui, S.Takagi, and H.Inoue,: "Surface polyfluorinated cationic vesicles."Phys. Chem. Chem. Phys., 1,3135-3140(1999).. 1. 3135-3146 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] T.Shinoda, T.Nishiwaki, and H.Inoue,: "Desulfonylation of Poly(4-hydroxystyrene sulfone) by Vapor Phase Silylation."J. Polym. Sci., A, Polym. Chem., 37,1549-1554(1999).. 37. 1549-1554 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 大町忠敏、日下裕美、高木慎介、井上晴夫: "ポリポリフルオロ化カチオン界面活性剤キャスト膜上における有機分子および水の吸着挙動"日本化学会誌、1999,451-456.. 451-456 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] S.Takagi and H.Inoue,: ""Molecular and Supramolecular Photochemistry of Porphyrins and Metalloporphyrins.""Mercel Dekker. 128 (1999)

    • Related Report
      1999 Annual Research Report

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

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