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1998 Fiscal Year Final Research Report Summary

One-Step Multi-electron Transfer for Molecular Conversion

Research Project

Project/Area Number 08044174
Research Category

Grant-in-Aid for international Scientific Research

Allocation TypeSingle-year Grants
SectionJoint Research
Research Field 高分子合成
Research InstitutionWaseda University

Principal Investigator

TSUCHIDA Eishun  Dept. Polym. Chem., Waseda Univ.. Professor, 理工学部, 教授 (90063461)

Co-Investigator(Kenkyū-buntansha) OYAIZU Kenichi  ARISE, Waseda Univ., Lecturer, 理工学総合研究センター, 講師 (90277822)
KOMATSU Teruyuki  ARISE, Waseda Univ., Lecturer, 理工学総合研究センター, 講師 (30298187)
NISHIDA Hiroyuki  Dept. Polym. Chem., Waseda Univ.. Professor, 理工学部, 教授 (90120930)
ANSON Fred C  Div. Chem. & Chem. Eng., Caltech (USA), Professor, Div Chem・ & Chem・ Eng・ ,, Professor
MIYATAKE Kenji  Dept. Polym. Chem., Waseda Univ., JSPS Fellow, 理工学研究科, 学振研究員 (50277761)
Project Period (FY) 1996 – 1998
Keywordsmulti-nuclear complex / oxidative polymarzation / oxygen 4-electron reduction / multi-electron transfer / polysulfonium / lipid porphyrin / photoelectron transfer / molecular assembly
Research Abstract

The research project aims at elucidating the multi-electron transfer process of oxygen molecules incorporated into the macromolecule-metal complexes, in order to establish novel molecular conversion processes which are promoted by the four-electron reduction of oxygen.
Followings have been established : Detailed analysis of the oxygen splitting reaction by one-step four-electron transfer, establishment of oxidative polymerization facilitated by multi-electron transfer process, elucidation of multi-electron transfer process in molecular assemblies. Based on these results, a general strategy to allow molecular conversions to proceed efficiently by multi-electron transfer process has been provided.
1. Multi-nuclear metal complexes that show one-step multi-electron transfer processes were synthesized and their structure was determined. A general method to provide a one-step multi-electron transfer was provided.
2. Oxygen splitting reaction by way of a μ-dioxo intermediate MOM-OO-MOM was established.
3. Synthesis of novel compounds, polysulfoniums and polythioethers, were established, and their properties were determined in detail.
4. Structure and properties of molecular assembly systems were elucidated, in terms of photoelectron transfer process.
5. Synthesis of high molecular-weight polyheteroacenes were established, and their physicochemical properties were determined.

  • Research Products

    (50 results)

All Other

All Publications (50 results)

  • [Publications] K. Oyaizu, K. Yamamoto, K. Yoneda, and E. Tsuchida: "Multielectron Redox Process of Vanadium Complexes in Oxidation of Low-Coordinate Vanadium(III) to Oxovanadium(V) with Dioxygen"Inorg. Chem.. 35. 6634-6635 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K. Yamamoto, K. Oyaizu, and E. Tsuchida: "Catalytic Cycle of a Divanadium Complex with Salen Ligands in O_2 Reduction : Two-Electron Redox Process of the Dinuclear Center"J. Am. Chem. Soc.. 118. 12665-12672 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] E. Tsuchida, K. Yamamoto, K. Miyatake, Y. Nishimura: "First Phenylene Polymers Linked by Sulfonium Groups"Angew. Chem., Int. Ed.. 35. 2843-2844 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K. Yamamoto, S. Kobayashi, E. Shouji, and E. Tsuchida: "Oxdative Coupling of Methyl Phenyl Sulfide via Sulfonium Formation Using an Oxovanadium Complex"J. Org. Chem.. 61. 1912-1913 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K. Yamamoto, K. Oyaizu, and E. Tsuchida: "Role of Multinuclear Complexes in Coordination and 4-Electron Reduction of Dioxygen"J. Inorg. Biochem.. 67. 390-390 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K. Yamamoto, K. Oyaizu, S. Kobayashi, E. Tsuchida: "Oxidation of Disulfides by 4-Electron Transfer to O_2 : A Ru(bpy)^<2+>_3 -Catalyzed Photo-Oxidation System for Selective Formation of Polythioethers"Phosphorus, Sulfur, and Silicon & The Related Elements. 120. 407-408 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] E. Tsuchida, K. Yamamoto, and K. Oyaizu: "Oxidative Polymerization of Pyrrole with a Vanadium Dinuclear Complex as a Two-Electron Redox Catalyst"J. Electroanal. Chem.. 438. 167-171 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K. Oyaizu and E. Tsuchida: "A Novel Decavanadium(V) Cluster with a Chiral Framework : [(O=V)_<10>(μ_2-O)_9(μ_3-O)_3(C_5H_7O_2)_6]Having an Approximate C_3 Symmetry"J. Am. Chem. Soc.. 120. 237-238 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] A. Haryono, K. Oyaizu, K. Yamamoto, J. Natori, E. Tsuchida: "Electrocatalytic Reduction of Dioxygen to Water by a Carbon Electrode Coated with (μ-Oxobis[(meso-tetraphenylporphyrinato)iron(III)] : a Convenient Template for Cofacially Oriented Iron(II) Porphyrins"Chem. Lett.. 233-234 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T. Komatsu, E. Tsuchida, C. Bo***cher, D. Donner, C. M****chmick, U. Siggel, W. Stocker, J. P. R*be, J.-H. Fuhrhop: "Solid Vesicle Membrane Made of meso-Tetrakis[(bixinylamino)-o-phenyl]porphyrins"J. Am. Chem. Soc.. 119. 11660-11665 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] E. Tsuchida, T. Komatsu: "Self-Organized Monolayer Assemblies of Octupusporphyrins : Photoinduced Electron Transfer and O_2-Coordination in Aqueous Media"Polym. Adv. Technol.. 9. 569-578 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K. Miyatake, E. Shouji, K. Yamamoto, E. Tsuchida: "Synsthesis and Proton Conductivity of Highly Sulfonated Poly(thiophenylene)"Macromolecules. 30. 2941-2946 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] E. Tsuchida, K. Yamamoto, K. Miyatake, K. Endo: "Molecular Assembly of Cholestrol-Bearing Poly(allyl amine) for Biding Salts in Water"Macromolecules. 30. 4235-4237 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K. Miyatake, Y. Yokoi, K. Yamamoto, E. Tsuchida: "A Selective and Efficient Synthesis of Cyclic Hexakis(thio-1, 4-phenylene) through Oxidative Polymerization of Diphenyl Disulfide"Macromolecules. 31. 403-407 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] E. Tsuchida, K. Miyatake: "Novel Synthesis of Polyarylenesulfonium Cations through a Multi-electron Transfer Process"Chin. J. Polym. Sci.. 106-116 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K. Oyaizu, A. Haryono, H. Yonemaru, E. Tsuchida: "Catalytic Behavior of a μ-Oxo Dimanganese(III) Octaethylporphyrin in O_2 Reduction"J. Chem. Soc., Faraday Trans.. 94. 3393-3399 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K. Oyaizu, A. Haryono, K. Yamamoto, J. Natori, E. Tsuchida: "(μ-Peroxo)bis[pyridine(phthalocyaninato)iron(III)] as a Convenient Catalyst for 4-Electron Reduction of Dioxygen"J. Chem. Soc., Faraday Trans.. 94. 3737-3742 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K. Miyatake, K. Yamamoto, Y. Yokoi, R. Tsuchida: "Novel Synthesis of Linear Perfluorinated Poly(Phenylene sulfide) from Aryl Sulfoxide"Macromolecules. 31. 403-407 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T. Tsuchida, K. Miyatake, K. Yamamoto, A. S. Hay: "Cyclic Arylene Sulfides : A Novel Synthesis and Ring-Opening Polymerization"Macromolecules. 31. 6469-6475 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K. Miyatake, K. Yamamoto, K. Endo, E. Tsuchida: "Superacidified Reaction of Sulfides and Esters for the Direct Synthesis of Sulfonium Derivatives"J. Org. Chem.. 63. 7522-7524 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y. Ding, A. R. Hlil, A. S. Hay, E. Tsuchida, K. Miyatake: "Syntheses of Semicrystalline Aromatic Poly(thioether thioether Ketone)s (PTTK and PTBTK) and Their Copolymers with Ether Analogues"Macromolecules. 32. 315-321 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] A. Haryono, K. Miyatake, E. Tsuchida: "Syntheses and Photochemical Reaction of Polyarylenesulfonium Salts"Macromol. Chem. Phys.. 200,(in press). (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] U. Bindig, C. Endisch, J.-H. Fuhrhop, T. Komatsu, E. Tsuchida, U. Siggel: "Optimized Polyelectrolyte Stabilization Procedures for Polymeric Porphyrin Assemblies in Water Allow the Analysis of Minute Photoreactivities"J. Colloid. & Interface Sci.. 199. 123-130 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T. Komatsu, T. Yanagimoto, E. Tsuchida, U. Siggel, J.-H. Fuhrhop: "Monolayer Assemblies Made of Octopusporphyrins with Pyridinium Head Groups : Electron Transfer Reaction in Non-covalent Porphyrin-Quinone Platelets in Aqueous Media"J. Phys. Chem.. 102. 6759-6765 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T. Osugi, Z.-C. Li, T. Komatsu, S. Takeoka, E. Tsuchida: "Photoexcitation and Electron Transfer Reactions of Zinc-Lipidporphyrins in DMSO"J. Porphyrins and Phthalocyanines. 2,(in press). (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K. Yamamoto, K. Oyaizu and E. Tsuchida: "Catalytic Cycle of a Divanadium Complex wilh Salen Ligands in OィイD12ィエD1 Reduction : Two-Electron Redox Process of the Dinuclear Center (salen=N,N'-Ethylenebis (salicylideneamine))"J. Am. Chem. Soc.. 118. 12665-12672 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Oyaizu, K. Yamamoto, K. Yoneda and E. Tsuchida: "Mulitielectron Redox Process of Vanadium Complexes in Oxidation of Low-coordinate Vanadium (III) to Oxovanadium (V) with Dioxygen"Inorg. Chem.. 35. 6634-6635 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] E. Tsuchida, K. Yamamoto, K. Oyaizu: "Oxidative Polymerization of Pyrrole with a Vanadium Dinuclear Complex as a Two-Electron Redox Catalyst"J. Electronal. Chem.. 438. 167-171 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] E. Tsuchida, K. Yamamoto, K. Miyake, Y. Nishimura: "First Phenylene Polymers Linked by Sulfonium Groups"Angew. Chem. Int. Ed. Engl.. 35. 2843-2845 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Yamamoto, S. Kobayashi, E. Shouji, E. Tsuchida: "Oxidative Coupling of Methly Phenul Sulfide via Sulfonium Formation Using an Oxovanadium Complex"J. Org. Chem.. 61. 1912-1913 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. Komatsu, E. Tsuchida, C. Boettcher, D. Donner, C. Messerschmidt, U. Siggel, W. Stocker, J. P. Rabe, J.-H. Fuhrhop: "Solid Membrane Made of meso-Tetra-o-anilinobixinamideporphyrins"J. Am. Chem. Soc.. 119. 11660-11665 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Oyaizu and E. Tsuchida: "A Novel Decavanadium (V) Cluster with a Chral Framework : [(O=V)ィイD210ィエD2(μィイD22ィエD2-O)ィイD29ィエD2(μィイD23ィエD2-O)ィイD23ィエD2(CィイD2ィエD2HィイD27ィエD2OィイD22ィエD2)ィイD26ィエD2] Having an ApproximateCィイD23ィエD2 Symmetry"J. Am. Chem. Soc.. 120. 237-238 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] A. Haryono, K. Oyaizu, K. Yamamoto, J. Natorim and E. Tsuchida: "Electrcatalytic Reduction of Dioxygen to Water by a Carbon Electrodecoated with (μ-Oxo)bis[(meso-tetraphenylporphyrinato)iron(III)] : a Convenient Template for Cofacially Oriented Iron (II) Porphyyrins"Chem. Lett.. 233-234 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Yamamoto, K. Oyaizu, S. Kobayashi and E. Tsuchida: "Oxidation of Disulfides by 4-Electron Tranfer to OィイD22ィエD2 : A Ru (bpy)ィイD2ィエD2ィイD12+ィエD1-Catalyzed Phot-Oxidation System for Selective Formation of Polythioethers"PhosPhorus, Sulfur, and Silicon & The Related Elements. 120 & 121. 407-408 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Yamamoto, K. Oyaizu and E. Tsuchida: "Role of Multinuclear Complexes in Coordination and 4-Electron Reduction of Dioxygen"J. Inorg. Biochem. 67. 390-390 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Miyatake, E. Shoji, K. Yamamoto, E. Tsuchida: "Synthesis and Proton Conductivity of Highly Sulfonated Poly(thio phenylene)"Macromolecules. 30. 2941-2946 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] E. Tsuchida, K. Yamamoto, K. Miyatake, K. Endo: "Molecular Assembly of Cholesterol-Bearing Poly(allyl amine) for Binding Bile Salts in Water"Macromolecules. 30. 4235-4237 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Miyatake, Y. Yokoi, K. Yamamoto, E. Tsuchida, A. S. Hay: "A Selective and Efficient Synthesis of Cyclic Hexakis(thio-1,4-phenylene) through Oxidative Polymerization of Diphenyl Disulfide"Macromolecules. 30. 4502-4503 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Miyatake, K. Yamamoto, Y. Yokoi, E. Tsuchida: "Novels Synthesis of Linear Perfluorinated Poly(phenylene sulfide) from Aryl Sulfoxide"Macromolecules. 31. 403-407 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. Ohgushi, Z. C. Li, T. Komatsu, S. Takeoka, E. Tsuchida: "Photoexcitation and Electron Transfer Reactions of Zinc-Lipidporphyrins in DMSO"J. Porphyrins and Phthalocyanines. 3. 1-7 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] E. Tsuchida, T. Komatsu, J.-H. Fuhrhop: "Self-Organized Monolayer Assemblies of Octopusporphyrins : Photoinduced Electron Tranfer and OィイD22ィエD2-Coordination in Aqueous Media"Polym. Adv. Technol. 9. 569-578 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Oyaizu, A. Haryono, H. Yonemaru, E. Tsuchida: "Catalyrtic Behavior of a μDxo Dimanganese (III) Octaethylporphyrin in OィイD22ィエD2 Reduction"J. Chem. Soc., Faraday Trans. 94. 3393-3399 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Oyaizu, A. Haryono, K. Yamamoto, J. Natori, E. Tsuchida: "(μ-Peroxo)bis[pyridine(phthalocyaninato)iron(III)] as a Convenient Catalyst for the 4-Electron Reduction of Dioxygen"J. Chem. Soc., Faraday Trans. 94. 3737-3742 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] E. Tsuchida, K. Miyatake: "Novel Synthesis of Polyarylenesulfonium Cations through a Multi-electron Transfer Process"Chin. J. Polym. Sci.. 16. 106-116 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] E.Tsuchida, K. Miyatake, K. Yamamoto, A. S. Hay: "Cyclic Arylene Sulfides : A Novel Synthesis and Ring-Opening Polymerization"Macromolecules. 31. 6469-6475 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Miyatake, K. Yamamoto, K. Endo, E. Tsuchida: "Superacidified Reaction of Sulfides and Esters for the Direct Synthesis of Sulfonium Derivatives"J. Org. Chem.. 63. 7522-7524 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] E. Tsuchida, K. Miyatake, Y. Ding, A. R. Hlil, A. S. Hay: "Syntheses of semicrystalline Aromatic Poly (thioether thioether ketone)s (PTTK and PTBTK) and Their Copolymers with Ether Analogues"Macromolecules. 32. 315-321 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] A. Haryono, K. Miyatake, E. Tsuchida: "Synthesis and Photochemical Reaction of Polyarylenesulfonium Salts"Macromol. Chem. Phys.. 200 (in press). (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] U. Bindig, C. Endisch, J.-H. Fuhrhop, T. Komatsu, E. TsuchidaU. Siggel: "Optimized Polyelectrolyte Stabilization Procedures for Polymeric Porphyrin Assembles in Water Allow the Analysis of Minute Photoreactivities"J. Colloid & Interface Sci.. 199. 123-130 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. Komatsu, T. Yanagimoto, E. Tsuchida, U. Siggel, J.-H. Fuhrhop: "Monolayer Assembles Made of Octopusporphyrins with Pyridinium Head Groups : Electron Transfer Reactions in Non-covalent Porphyrin-Quinone Platelets in Aquenous Media"J. Phys. Chem. 102. 6759-6765 (1998)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 2001-10-23  

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