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Photo-Induced Spin Alignment Using Photo-Excited High-Spin State of π-Conjugated Stable Radicals

Research Project

Project/Area Number 13440211
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field 機能・物性・材料
Research InstitutionOsaka City University

Principal Investigator

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

Project Period (FY) 2001 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥15,700,000 (Direct Cost: ¥15,700,000)
Fiscal Year 2003: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 2002: ¥5,300,000 (Direct Cost: ¥5,300,000)
Fiscal Year 2001: ¥8,800,000 (Direct Cost: ¥8,800,000)
KeywordsMolecular Magnetism / Photo-Induced Spin Alignment / π-Conjugated Spin System / High-Spin Excited State / Stable Radical / π-Topology / Charge Transfer Complex / Photo-Induced Spin Coupler / 動的スピン分極 / 電荷移動相互作用 / 光励起高スピン状態 / 励起五重項状態 / 有機電荷移動結晶 / π共役安定ラジカル / 時間分解ESR / アントラセン誘導体 / フェルダジルラジカル
Research Abstract

This project was carried out in order to clarify the electronic structure and the dominant mechanism of the spin alignment in the photo-excited states of π-conjugated organic multi-spin systems. The following new findings were obtained through this project.
(1)According to the proposal, we make up the transient absorption spectroscopy apparatus as well as the time-resolved fluorescence measurement system attached with variable temperature system. The life-times of the photo-excited high-spin organic systems were determined to be ca. 10-20 μs at 77 K using this apparatus.
(2)The photo-excited quartet and quintet high-spin states of the verdazyl radical systems have been first detected. The photo-excited quartet high-spin state was also detected for the pyrene-verdazyl radical. Based on these results, the necessary conditions to obtain the photo-excited high-spin state have been clarified in detail and succeeded to establish the guiding principles for the molecular designing of organic spi … More n system with the high-spin photo-excited state.
(3)The role of π-topology in the spin alignment on the photo-excited state has been proven by studying the photo-excited states of π-conjugated Anthracene-t-Butyl-Nitroxide radicals.
(4)A unique lowest triplet photo-excited state constructed from four unpaired electrons was detected for the first time by the proper molecular design taking π-topology into account. The magnitude of the fine-structure parameters is reduced by the antiferromagnetic intramolecular spin alignment.
(5)The stable radicals with photo-excited high-spin states, which electron donor property was improved by attaching dimethylamino group were synthesized and their electronic states and physical properties were investigated. One of the problems was solved, which are concerned with the construction of the charge-transfer complexes using the π-conjugated organic spin systems with the photo-excited high-spin states.
(6)In order to investigate the possibility of LIESST using organic spin systems, we synthesized several charge-transfer complexes constructed from the π-conjugated organic spin systems with the photo-excited high-spin states and the proper electron accepters. Their basic physical and optical properties as well as the electronic structures were clarified by ESR, time-resolved ESR, optical absorption, and SQUID measurements. Less

Report

(4 results)
  • 2003 Annual Research Report   Final Research Report Summary
  • 2002 Annual Research Report
  • 2001 Annual Research Report
  • Research Products

    (21 results)

All 2005 2004 2002 2001 Other

All Journal Article (16 results) Publications (5 results)

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

    • Author(s)
      Y.Teki
    • Journal Title

      Polyhedron (accepted)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [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 (accepted)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] The Exploration of Magnetic Photo-Excited States Using Organometallic Spin Couplers Based on the Silore Ring2004

    • 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
      2003 Final Research Report Summary
  • [Journal Article] Excited Hi-Spin Quartet(S=3/2) State of a Novel π-Conjugated Organic Spin System, Pyrene-Verdazyl Radical.2004

    • 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(和文)」より
    • Related Report
      2003 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

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] The Exploration of Magnetic Photo-Excited States Using Organometallic Spin Couplers Based on the Silore Ring2004

    • 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
      2003 Final Research Report Summary
  • [Journal Article] Excited High-Spin Quartet (S=3/2) State of a Novel π-Conjugated Organic Spin System, Pyrene-Verdazyl Radical.2004

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

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

      Pages: 95-99

    • NAID

      10011835882

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 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

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Excited High-Spin States of Novel π Conjugated Verdazyl Radicals : Photoinduced Spin Alignment Utilizing the Excited Molecular Field.2002

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

      Mol.Phys. 100

      Pages: 1385-1394

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Spin Alignment between the Triplet Excited State of Phenylanthracene and the Dangling Verdazyl Radical as Studied by Time-Resolved Electron Spin Resonance.2001

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

      Int.J.Mod.Phys.B 15

      Pages: 4029-4031

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Photo-Induced Spin Alignment Utilizing the Excited Molecular Field between the Excited Triplet State of Phenyl- or Diphenylanthracene and the Dangling Nitroxide Radicals : Theoretical Investigation of the Mechanisum for the Intramolecular Spin Alignment2001

    • Author(s)
      Y.Teki
    • Journal Title

      Polyhedron 20

      Pages: 1163-1168

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Photo-Induced Spin Alignment Utilizing the Excited Molecular Field between the Excited Triplet State of Phenyl- or Diphenylanthracene and the Dangling Nitroxide Radicals : Theoretical Investigation of the Mechanism for the Intramolecular Spin Alignment2001

    • Author(s)
      Y.Teki
    • Journal Title

      Polyhedron 20

      Pages: 1163-1168

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Design, Synthesis and Physical Property of a π-Conjugated Photo-excited Organic High-Spin Systems toward the Functional Material

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

      Polyhedron (accepted)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Topology and Spin Alignment Utilizing the Excited Molecular Field in π-Conjugated Organic Spin Systems

    • Author(s)
      Y.Teki
    • Journal Title

      Polyhedron (accepted.)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [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 Complex

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

      Polyhedron (accepted.)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Journal Article] Design, Synthesis and Physical Property of a π-Conjugated Photo-excited Organic High-Spin Systems toward the Functional Material

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

      Polyhedron (accepted.)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Y.Teki, M.Kimiura, S.Narimatsu, K.Ohara, K.Mukai: "Excited High-Spin Quartet (S=3/2) State of a Novel π-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.Teki, M.Nakatsuji, Y.Miura: "Excited High-Spin States of Novel π-Conjugated Verdazyl Radicals : Photo-Induced Spin Alignment Utilizing the Excited Molecular Field"Molecular Physics. 100. 1385-1394 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Y.Teki: "Photo-Induced Spin Alignment Utilizing the Excited Molecular Field between the Excited Triplet State of Phenyl-or Diphenylanthracene and the Dangling Nitroxide Radicals : Theoretical Investigation of the Mechanism for the Intramolecular Spin Alignment"Polyhedron. 20. 1163-1168 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Y.Teki, M.Nakatsuji, Y.Miura: "Excited High-Spin States of Novel pi-Conjugated Verdazyl Radicals : Photo-Induced Spin Alignment Utilizing the Excited Molecular Field"Molecular Physics. (in press). (2002)

    • Related Report
      2001 Annual Research Report

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Published: 2001-04-01   Modified: 2016-04-21  

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