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Origin of the highly efficient electroluminescence as studied by Time-resolved EPR

Research Project

Project/Area Number 15350074
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Functional materials chemistry
Research InstitutionTohoku University

Principal Investigator

AKIYAMA Kimio  Tohoku University, Institute of multidisciplinary research for advanced materials, Associate professor, 多元物質科学研究所, 助教授 (10167851)

Co-Investigator(Kenkyū-buntansha) IKOMA Tadaaki  Tohoku University, Institute of multidisciplinary research for advanced materials, Assistant professor, 多元物質科学研究所, 助手 (10212804)
Project Period (FY) 2003 – 2005
Project Status Completed (Fiscal Year 2005)
Budget Amount *help
¥13,600,000 (Direct Cost: ¥13,600,000)
Fiscal Year 2005: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 2004: ¥3,700,000 (Direct Cost: ¥3,700,000)
Fiscal Year 2003: ¥8,700,000 (Direct Cost: ¥8,700,000)
Keywordselectroluminescence / excited triplet state / electron spin resonance / intersystem crossing / 時間分解EPR / 共役高分子 / 電子スピン
Research Abstract

The research was carried out to elucidate the mechanisms of highly efficient electroluminescence in organic dyes and π-conjugated polymers systems. Using by time-resolved EPR technique polarized EPR spectra were observed both in the rigid matrices and film samples at low temperature. The paramagnetic species generated by the irradiation were assigned to their excited triplet states, followed by the reverse intersystem crossing (RISC) from their higher excited triplet state upon excitation by the second laser pulse. The RISC yields were determined for several organic dyes from the two-color two-laser TREPR experiments. The signals due to radical pairs were also obtained and analyzed in terms of the spin correlated radical pair mechanism. The results gave the information on the relaxation processes in excited states of organic dyes and π-conjugated polymers and the electronic structures of the transient radical pair species, playing important roles in the charge transport processes.
The metal (Ir and Pt) complexes were also of the subject because of their high quantum yields of the phosphorescence induced by the large spin-orbit coupling (SOC) interactions. No TREPR signals were obtained in the system of Ir and Pt complexes even at cryogenic temperatures. The facts were interpreted by the large SOC leading to disturb the observation of triplet EPR spectra because of large dipole-dipole interactions and also the effective relaxation in their excited states. To obtain the information on the excited triplet states of these metal complexes the EPR measurements were carried out to observe the ion radical species, which were expected to have similar electronic properties with corresponding excited triplet states, generated by the electrochemical method at room temperature. Although the optimum experimental conditions such as solvents and/or applied voltages for electrolysis of the samples were examined, no significant signals were observed.

Report

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

    (45 results)

All 2005 2004 2003 Other

All Journal Article (40 results) Publications (5 results)

  • [Journal Article] Carrier Generation in Photoconductive Poly(N-vinylcarbazole) as Revealed by Multifrequency Time-resolved ESR.2005

    • Author(s)
      Tadaaki Ikoma
    • Journal Title

      Phys. Rev. B 71・15

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Photoinduced ω-Bond Dissociation in the Higher Excited Singlet (S_2) and Lowest Triplet (T_1) States of a Benzophenone Derivative in Solution2005

    • Author(s)
      Minoru Yamaji
    • Journal Title

      J. Phys. Chem. A 109・17

      Pages: 3843-3848

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Anisotropic Interfacial Electron Transfer Across a Semiconductor-Solution Interface Studied by Time-Resolved EPR2005

    • Author(s)
      Kimio Akiyama
    • Journal Title

      Angew. Chem. Int. Ed. 44・23

      Pages: 3591-3594

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Spin Dynamic Study on the Electric Field Dependence of Carrier Generation.2005

    • Author(s)
      Fuyuki Ito
    • Journal Title

      J. Phys. Chem. B. 109・15

      Pages: 7208-7213

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Carrier Generation Process on Photoconductive Polymer Films as Studied by Magnetic Field Effects on the Charge-Transfer Fluorescence and Photocurrent2005

    • Author(s)
      Fuyuki Ito
    • Journal Title

      J. Phys. Chem. B. 109・15

      Pages: 8707-8717

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Divergent Oxidative Rearrangements in Solution and in a Zeolite : Distal vs Proximal Bond Cleavage of Methylenecyclopropanes2005

    • Author(s)
      Hiroshi Ikeda
    • Journal Title

      J. Am. Chem. Soc. 127・41

      Pages: 14497-14504

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Spin dynamics of carrier generation in a photoconductive C_<60>-doped poly (N-vinylcarbazole) film2005

    • Author(s)
      Toshinari Ogiwara
    • Journal Title

      Chem. Phys. Lett. 411・4-6

      Pages: 378-383

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Primary Charge-recombination in an Artificial Photosynthetic Reaction Center.2005

    • Author(s)
      Yasuhiro Kobori
    • Journal Title

      Proc. Nat. Acad. Sci. USA 102

      Pages: 10017-10022

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Carrier Generation in Photoconductive Poly(N-vinylcarbazole) as Revealed by Multifrequency Time-resolved ESR.2005

    • Author(s)
      Tadaaki Ikoma
    • Journal Title

      Phys.Rev.B 71(15)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Photoinduced ω-Bond Dissociation in the Higher Excited Singlet (S_2) and Lowest Triplet (T_1) States of a Benzophenone Derivative in Solution2005

    • Author(s)
      Minoru Yamaji
    • Journal Title

      J.Phys.Chem.A 109(17)

      Pages: 3843-3848

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Anisotropic Interfacial Electron Transfer Across a Semiconductor-Solution Interface Studied by Time-Resolved EPR2005

    • Author(s)
      Kimio Akiyama
    • Journal Title

      Angew Chem.Int.Ed. 44(23)

      Pages: 3591-3594

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Spin Dynamic Study on the Electric Field Dependence of Carrier Generation.2005

    • Author(s)
      Fuyuki Ito
    • Journal Title

      J.Phys.Chem.B. 109(15)

      Pages: 7208-7213

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Carrier Generation Process on Photoconductive Polymer Films as Studied by Magnetic Field Effects on the Charge-Transfer Fluorescence and Photocurrent2005

    • Author(s)
      Fuyuki Ito
    • Journal Title

      J.Phys.Chem.B 109(15)

      Pages: 8707-8717

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Divergent Oxidative Rearrangements in Solution and in a Zeolite : Distal vs Proximal Bond Cleavage of Methylenecyclopropanes2005

    • Author(s)
      Hiroshi Ikeda
    • Journal Title

      J.Am.Chem.Soc. 127(41)

      Pages: 14497-14504

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Spin dynamics of carrier generation in a photoconductive C_<60>-doped poly(N-vinylcarbazole) film2005

    • Author(s)
      Toshinari Ogiwara
    • Journal Title

      Chem.Phys.Lett. 411(4-6)

      Pages: 378-383

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Primary Charge-recombination in an Artificial Photosynthetic Reaction Center2005

    • Author(s)
      Yasuhiro Kobori
    • Journal Title

      Proc.Nat.Acad.Sci.USA 102

      Pages: 10017-10022

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Anisotropic Interfacial Electron Transfer Across a Semiconductor-Solution Interface Studied by Time-Resolved EPR2005

    • Author(s)
      Kimio Akiyama
    • Journal Title

      Angew.Chem.Int.Ed 44・23

      Pages: 3591-3594

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Photoinduced □-Bond Dissociation in the Higher Excited Singlet(S_2) and Lowest Triplet (T_1) States of a Benzophenone Derivative in Solution2005

    • Author(s)
      Yamaji Minoru
    • Journal Title

      J.Phys.Chem.A 109・17

      Pages: 3843-3848

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Carrier Generation in Photoconductive Poly(N-vinylcarbazole) as Revealed by Multifrequency Time-resolved ESR2005

    • Author(s)
      Tadaaki Ikoma
    • Journal Title

      Phys.Rev.B 71・15

    • Related Report
      2005 Annual Research Report
  • [Journal Article] spin Dynamic Study on the Electric Field Dependence of Carrier Generation2005

    • Author(s)
      Fuyuki Ito
    • Journal Title

      J.Phys.Chem.B 109・15

      Pages: 7208-7213

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Carrier Generation Process on Photoconductive Polymer Films as Studied by Magnetic Field Effects on the Charge-Transfer Fluorescence and Photocurrent2005

    • Author(s)
      Fuyuki Ito
    • Journal Title

      J.Phys.Chem.B 109・18

      Pages: 8707-8717

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Primary Charge-recombination in an Artificial Photosynthetic Reaction Center.2005

    • Author(s)
      Yasuhiro Kobori
    • Journal Title

      Proc.Nat.Acad.Sci.USA 102

      Pages: 10017-10022

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Anisotropic Interfacial Electron Transfer Across a Semiconductor-Solution Interface Studied by Time-Resolved EPR2005

    • Author(s)
      Kimio Akiyama
    • Journal Title

      Angew.Chem.Int.Ed. 44(in Press)(印刷中)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Rearrangement of a 2-Methylenecyclobutanone Derivative Triggered by Photoinduced Electron Transfer : An Unprecedented Oxa Analogue of the Tetramethyleneethane Radical Cation2004

    • Author(s)
      Hiroshi Ikeda
    • Journal Title

      J. Am. Chem. Soc. 126・2

      Pages: 414-415

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Superexchange Electron Tunneling Mediated by Solvent Molecules : Pulsed Electron Paramagnetic Resonance Study on Electronic Coupling in Solvent-Separated Radical Ion Pairs.2004

    • Author(s)
      Yasuhiro Kobori
    • Journal Title

      J. Phys. Chem. B 108・29

      Pages: 10226-10240

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Photoinduced Electron-Transfer, Pyrolyses, and Direct Irradiation Reactions of 2-Methylenecyclobutanones : Regioselective Bond Cleavage Depends on the Substituents and the Method of Activation.2004

    • Author(s)
      Hiroshi Ikeda
    • Journal Title

      Euro. J. Org. Chem. 7

      Pages: 1500-1508

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Aspects of the Electron Transfer Reaction Rate for Systems Accompanying a Chemical Equilibrium Change.2004

    • Author(s)
      Tomoaki Yago
    • Journal Title

      Bull. Chem. Soc. Jpn. 77・11

      Pages: 1997-2001

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Rearrangement of a 2-Methylenecyclobutanone Derivative Triggered by Photoinduced Electron Transfer : An Unprecedented Oxa Analogue of the Tetramethyleneethane Radical Cation2004

    • Author(s)
      Hiroshi Ikeda
    • Journal Title

      J.Am.Chem.Soc. 126(2)

      Pages: 414-415

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Superexchange Electron Tunneling Mediated by Solvent Molecules : Pulsed Electron Paramagnetic Resonance Study on Electronic Coupling in Solvent-Separated Radical Ion Pairs.2004

    • Author(s)
      Yasuhiro Kobori
    • Journal Title

      J.Phys.Chem.B. 108(29)

      Pages: 10226-10240

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Photoinduced Electron-Transfer, Pyrolyses, and Direct Irradiation Reactions of 2-Methylenecyclobutanones : Regioselective Bond Cleavage Depends on the Substituents and the Method of Activation.2004

    • Author(s)
      Hiroshi Ikeda
    • Journal Title

      Euro.J.Org.Chem. (7)

      Pages: 1500-1508

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Aspects of the Electron Transfer Reaction Rate for Systems Accompanying a Chemical Equilibrium Change.2004

    • Author(s)
      Tomoaki Yago
    • Journal Title

      Bull.Chem.Soc.Jpn. 77(11)

      Pages: 1997-2001

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Rearrangement of a 2-Methylenecyclobutanone Derivative Triggered by Photoinduced Electron Transtfer : An Unprecedented Oxa Analogue of the Tetramethyleneethane Radical Cation2004

    • Author(s)
      Hiroshi Ikeda
    • Journal Title

      J.Am.Chem.Soc. 126・2

      Pages: 414-415

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Superexchange Electron Tunneling Mediated by Solvent Molecules Pulsed Electron Paramagnetic Resonance Study on Electronic Coupling in Solvent-Separated Radical Ion Pairs.2004

    • Author(s)
      Yasuhiro Kobori
    • Journal Title

      J.Phys.Chem.B 108・29

      Pages: 10226-10240

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Photoinduced Electron-Transfer, Pyrolyses, and Direct Irradiation Reactions of 2-Methylenecyclobutanones : Regioselective Bond Cleavage Depends on the Substituents and the Method of Activation.2004

    • Author(s)
      Hiroshi Ikeda
    • Journal Title

      Euro.J.Org.Chem. 7

      Pages: 1500-1508

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Spin Trapping of ^<13>C-Labeled p-Benzynes Generated by Masamune-Bergman Cyclization of Bicyclic Nine-Membered Enediynes.2004

    • Author(s)
      Toyonobu Usuki
    • Journal Title

      Angew.Chem.Int.Ed. 43・39

      Pages: 5249-5253

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Aspects of the Electron Transfer Reaction Rate for Systems Accompanying a Chemical Equilibrium Change.2004

    • Author(s)
      Tomoaki Yago
    • Journal Title

      Bull.Chem.Soc.Jpn. 77・11

      Pages: 1997-2001

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Time-resolved (TR) EPR Study of the First Excited Triplet States of Dibenzocycloheptadienylidene and Diphenylmethylene derivatives2003

    • Author(s)
      Kimio AKIYAMA
    • Journal Title

      J. Phys. Chem A. 107・10

      Pages: 1447-1451

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Two-laser Two-color Time-resolved EPR Study on Higher-excited-state Triplet-singlet Intersystem Crossing of Porphyrins and Phthalocyanines.2003

    • Author(s)
      Yoshiyuki KAMATA
    • Journal Title

      Appl. Magn. Reson 21

      Pages: 409-421

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Time-resolved (TR) EPR Study of the First Excited Triplet States of Dibenzocycloheptadienylidene and Diphenylmethylene derivatives2003

    • Author(s)
      Kimio Akiyama
    • Journal Title

      J.Phys.Chem A. 107(10)

      Pages: 1447-1451

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Two-laser Two-color Time-resolved EPR Study on Higher-excited-state Triplet-singlet Intersystem Crossing of Porphyrins and Phthalocyanines.2003

    • Author(s)
      Yoshiyuki Kamata
    • Journal Title

      Appl.Magn.Reson. 21

      Pages: 409-421

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Publications] Kimio AKIYAMA: "Time-resolved(TR)EPR Study of the First Excited Triplet States of Dibenzocycloheptadienylidene_and Diphenylmethylene derivatives"J.Phys.Chem A.. 107(10). 1447-1451 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Yoshiyuki KAMATA: "Two-laser Two-color Time-resolved EPR Study on Higher-excited-state Triplet singlet Intersystem Crossing of Porphyrins and Phthalocyanines"Appl.Magn.Reson. 21. 409-421 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Tadaaki IKOMA: "Angle-selective Measurements of Spin Soliton in Ladder Polydiacetylene by Pulsed 94 GHz EPR"Appl.Magn.Reson. 21. 445-453 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Fuyuki ITO: "Long-range Jump versus Stepwise Hops : Magnetic Field Effects on the Charge-transfer Fluorescence from Photoconductive Polymer Films"J.Am Chem.Soc.. 125(16). 4722-4723 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Yasutomo NAGANO: "Symmetry Switching of the Fluorescent Excited State in α,ω-Diphenylpolyynes/"J.Am.Chem.Soc.. 125(16). 14103-14112 (2003)

    • Related Report
      2003 Annual Research Report

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Published: 2003-04-01   Modified: 2016-04-21  

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