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Spin Alignment of π-Conjugated Spin Systems Using the Dynamics

Research Project

Project/Area Number 15087208
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionOsaka City University

Principal Investigator

TEKI Yoshio  Osaka City University Department of Material Science, Professor, 大学院理学研究科, 教授 (00180068)

Co-Investigator(Kenkyū-buntansha) MIURA Yozo  Osaka City University, Department of Applied Chemistry, Professor, 大学院工学研究科, 教授 (50047312)
Project Period (FY) 2003 – 2006
Project Status Completed (Fiscal Year 2006)
Budget Amount *help
¥37,400,000 (Direct Cost: ¥37,400,000)
Fiscal Year 2006: ¥7,000,000 (Direct Cost: ¥7,000,000)
Fiscal Year 2005: ¥10,500,000 (Direct Cost: ¥10,500,000)
Fiscal Year 2004: ¥10,600,000 (Direct Cost: ¥10,600,000)
Fiscal Year 2003: ¥9,300,000 (Direct Cost: ¥9,300,000)
Keywordsπ-radicals / photo-excited high spin state / dynamic electron polarization / photo-induced spin alignment / photo-induced electron transfer / ion-pair state / time-resolved ESR / charge transfer / イオン対 / 時間分解ESR / 光合成系 / 分子磁性 / 光励起状態 / スピン整列 / 電子移動 / エネルギー移動 / π共役系 / パルスESR / 光励起高スピン状態 / π共役スピン系 / スピンダイナミックス / 電荷移動錯体 / πトポロジー / 光誘起磁性 / 有機電荷移動錯体 / 分子素子
Research Abstract

In this project, we have obtained the following two representative results.
(1)We have obtained the first evidence of the photo-excited quartet state with a unique dynamic electron polarization (DEP) generated through the ion-pair state (charge separated state). The ion-pair state is generated by the intramolecular photo-induced electron transfer from the anthracene moiety to the bodipy functional component. Such a unique DEP pattern has been reported only for the triplet states of the photosystems I, II and the model compounds. This is the first detection of the unique DEP pattern detected in the quartet high-spin state.
(2)We have also succeeded to detect a novel lowest photo-excited triplet (S=1) state arising from four unpaired electrons. The low-lying quintet (S=2) photo-excited state was located above the photo-excited triplet state. The unique triplet state has D value reduced by the antiferromagnetic spin alignment between two radical spins through the excited triplet spin coupler. The general theoretical predictions of the spin alignment and the reduction of the fine-structure splitting of the radical-triplet-radical system are presented.
In addition to the above results, we investigated several charge-transfer complexes, in which the electron donor parts are the π-radicals with the photo-excited quartet high-spin states. We also clarified the magnetic properties of the some metal complexes using the photo-excited high-spin organic molecules as ligands. Furthermore, we studied the spin dynamics of the photo-excited high-spin states of the π-radicals using a pulsed ESR technique combined with a pulsed LASER excitation.

Report

(5 results)
  • 2006 Annual Research Report   Final Research Report Summary
  • 2005 Annual Research Report
  • 2004 Annual Research Report
  • 2003 Annual Research Report
  • Research Products

    (30 results)

All 2007 2006 2005 2004 Other

All Journal Article (25 results) Publications (5 results)

  • [Journal Article] Design, synthesis and physical properties of the metal complexes using π-radical with photo-excited high-spin state as a ligand2007

    • Author(s)
      H.Tamekuni, Y.Teki
    • Journal Title

      Polyhedron 26(In press)

    • Related Report
      2006 Annual Research Report
  • [Journal Article] The Metal Complexes using Organic Ligands with Photo-Excited High-Spin States2007

    • Author(s)
      N.Mihara, Y.Teki
    • Journal Title

      Polyhedron 26(In press)

    • Related Report
      2006 Annual Research Report
  • [Journal Article] First evidence for a uniquely spin polarized quartet photo-excited state of π-conjugated organic spin system generated through ion pair state2006

    • Author(s)
      Y.Teki, H.Tamekuni, J.Takeuchi, Y.Miura
    • Journal Title

      Angew.Chem.Int.Ed. 45

      Pages: 4666-4670

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Towards a better understanding of photo-excited spin alignment processes using silole diradicals2006

    • Author(s)
      N.Roques, P.Gerbier, Y.Teki et al.
    • Journal Title

      New J.Chem. 30

      Pages: 1319-1327

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] π-Topology and spin alignment in unique photo-excited triplet and quintet states arising from four unpaired electrons of an organic spin system2006

    • Author(s)
      Y.Teki, T.Toichi, S.Nakajima
    • Journal Title

      Chem.Eur.J. 12

      Pages: 2329-2336

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Syntheses and magnetic properties of Cu(II)(hfac)2 and Mn(II)(hfac)2 complex es of 4-pyridyl-substituted thioaminyl radicals2006

    • Author(s)
      Y.Miura, I.Kato, Y.Teki
    • Journal Title

      Dalton Trans.

      Pages: 961-966

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Towards a better understanding of photo-excited spin alignment processes using silole diradicals2006

    • Author(s)
      N.Roques, P.Gerbier*, Y.Teki* et al.
    • Journal Title

      New J. Chem. 30

      Pages: 1319-1327

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] First evidence for a uniquely spin polarized quartet photo-excited state of π-conjugated organic spin system generated through ion pair state2006

    • Author(s)
      Y.Teki*, H.Tamekuni, J.Takeuchi, Y.Miura
    • Journal Title

      Angew. Chem. Int. Ed. 45

      Pages: 4666-4670

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] π-Topology and spin alignment in unique photo-excited triplet and quintet states arising from four unpaired electrons of an organic spin system2006

    • Author(s)
      Y.Teki*, T.Toichi, S.Nakajima
    • Journal Title

      Chem. Eur. J. 12

      Pages: 2329-2336

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Syntheses and magnetic properties of Cu(II)(hfac)2 and Mn(II)(hfac)2 complexes of 4-pyridyl-substituted thioaminyl radicals2006

    • Author(s)
      Y.Miura*, I.Kato, Y.Teki*
    • Journal Title

      Dalton Trans

      Pages: 961-966

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] New Method for Syntheses of N-tert-Alkoxyarylaminyl Radicals2006

    • Author(s)
      Y.Miura, Y.Muranaka, Y.Teki
    • Journal Title

      J. Org. Chem. 71

      Pages: 4786-4794

    • Related Report
      2006 Annual Research Report
  • [Journal Article] First Evidence for a Uniquely Spin Polarized Quartet Photo-Excited State of pi-Conjugated Organic Spin System Generated Through Ion Pair State2006

    • Author(s)
      Y.Teki, H.Tamekuni, J.Takeuchi, Y.Miura
    • Journal Title

      Angew. Chem. Int. Ed. 45

      Pages: 4666-4670

    • Related Report
      2006 Annual Research Report
  • [Journal Article] π-Topology and Spin Alignment in Unique Photo-Excited Triplet and Quintet States Arising from Four Unpaired Electrons of an Organic Spin System.2006

    • Author(s)
      Y.Teki, T.Toichi, S.Nakajima
    • Journal Title

      Chem.Eur.J. 12

      Pages: 2329-2336

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Syntheses and magnetic properties of Cu(II)(hfac)2 and Mn(II)(hfac)2 complexes of 4-pyridyl-substituted thioaminyl radicals.2006

    • Author(s)
      Y.Miura, I.Kato, Y.Teki
    • Journal Title

      Dalton Trans.

      Pages: 961-966

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Topology and Spin Alignment Utilizing the Excited Molecular Field in π-Conjugated Organic Spin Systems2005

    • Author(s)
      Y.Teki
    • Journal Title

      Polyhedron 24

      Pages: 2299-2308

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Design, Synthesis and Physical Property of a π-Conjugated Photo-excited Organic High-Spin Systems toward the Functional Material2005

    • Author(s)
      T.Toichi, Y.Teki
    • Journal Title

      Polyhedron 24

      Pages: 2337-2340

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Design, Synthesis and Electronic States of an Iminonitroxide Radical with Excited Quartet High-Spin State and Photo-Induced Electron Transfer in Its CT Complex2005

    • Author(s)
      Y.Teki, S.Nakajima
    • Journal Title

      Polyhedron 24

      Pages: 2185-2188

    • Related Report
      2005 Annual Research Report
  • [Journal Article] The exploration of magnetic photo-excited states using organometallic spin couplers based on the silore ring.2004

    • Author(s)
      N.Roques, Ph.Gerbier, S.Nakajima, Y.Teki, C.Guerin
    • Journal Title

      J.Phys.Chem.Solid. 65

      Pages: 759-762

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Excited high-spin quartet(S = 3/2)state of a novel π-conjugated organic spin system, pyrene-verdazyl radical2004

    • Author(s)
      Y.Teki, M.Kimura, S.Narimatsu, K.Ohara, K.Mukai
    • Journal Title

      Bull.Chem.Soc.Jpn.(Selected Paper) 71

      Pages: 95-99

    • NAID

      10011835882

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] The exploration of magnetic photo-excited states using organometallic spin couplers based on the silore ring.2004

    • Author(s)
      N.Roques, Ph.Gerbier*, S.Nakajima, Y.Teki, C.Guerin
    • Journal Title

      J. Phys. Chem. Solid. 65

      Pages: 759-762

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Excited high-spin quartet (S = 3/2) state of a novel n-conjugated organic spin system, pyrene-verdazyl radical2004

    • Author(s)
      Y.Teki*, M.Kimura, S.Narimatsu, K.Ohara, K.Mukai*
    • Journal Title

      Bull. Chem. Soc. Jpn. (Selected Paper) 71

      Pages: 95-99

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Novel Photo-excited Triplet State Arising from Four Unpaired Electrons: π-Topology and Spin Alignment in Excited State of Organic Spin System2004

    • Author(s)
      Y.Teki, S.Nakajima
    • Journal Title

      Chem. Lett. 33

      Pages: 1500-1501

    • NAID

      10013772217

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Topology and Spin Alignment Utilizing the Excited Molecular Field in π-Conjugated Organic Spin Systems2004

    • Author(s)
      Y.Teki
    • Journal Title

      Polyhedron (accepted)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Design, Synthesis and Electronic States of an Iminonitroxide Radical with Excited Quartet High-Spin State and Photo-Induced Electron Transfer in Its CT Complex2004

    • Author(s)
      Y.Teki, S.Nakajima
    • Journal Title

      Polyhedron (accepted)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Design, Synthesis and Physical Property of a π-Conjugated Photo-excited Organic High-Spin Systems toward the Functional Material2004

    • Author(s)
      T.Toichi, Y.Teki
    • Journal Title

      Polyhedron (accepted)

    • Related Report
      2004 Annual Research Report
  • [Publications] Y.Teki, M.Kimura, S.Narimatsu, K.Ohara, K.Mukai: "Excited High-Spin Quartet (S=3/2) State of a Novel □-Conjugated Organic Spin System, Pyrene-Verdazyl Radical"Bull.Chem.Soc.Jpn.(Selected Paper). 77. 95-99 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] N.Roques, P.Gerbier, S.Nakajima, Y.Teki, C.Guerin: "The Exploration of Magnetic Photo-Excited States Using Organometallic Spin Couplers Based on the Silore Ring"J.Phys.Chem.Solid.. 65. 759-762 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] Y.Miura, T.Nishi, Y.Teki: "ESR Studies of Nitrogen-Centered Free Radicals, part 58. Isolation and Magnetic Properties of Heterocycle-Carrying N-Alkoxyarylaminyl Radicals"J.Org.Chem.. 68. 10158-10161 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Y.Miura, Y.Nakamura, Y.Teki: "ESR Studies of Nitrogen-Centered Free Radicals, part 57. Ferromagnetic Behavior of Formyl-Group-Carrying Stable Thioaminyl Radicals"J.Org.Chem.. 68. 8244-8247 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Y.Miura, Y.Oyama, Y.Teki: "Magnetic Interaction of Pyridyl-Substituted Thioaminyl Stable Free Radical"J.Org.Chem.. 68. 1225-1234 (2003)

    • Related Report
      2003 Annual Research Report

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Published: 2003-04-01   Modified: 2018-03-28  

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