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Structural Study of Photo-Induced Phenomena in Crystals by Synchrotron Radiation Crystallography

Research Project

Project/Area Number 14340187
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Physical chemistry
Research InstitutionUniversity of Hyogo (2004)
Himeji Institute of Technology (2002-2003)

Principal Investigator

TORIUMI Koshiro  University of Hyogo, Graduate School of Material Science, Professor, 大学院・物質理学研究科, 教授 (90124221)

Co-Investigator(Kenkyū-buntansha) OZAWA Yoshiki  University of Hyogo, Graduate School of Material Science, Associate Professor, 大学院・物質理学研究科, 助教授 (40204200)
MITSUMI Minoru  University of Hyogo, Graduate School of Material Science, Research Associate, 大学院・物質理学研究科, 助手 (20295752)
Project Period (FY) 2002 – 2004
Project Status Completed (Fiscal Year 2004)
Budget Amount *help
¥12,200,000 (Direct Cost: ¥12,200,000)
Fiscal Year 2004: ¥1,900,000 (Direct Cost: ¥1,900,000)
Fiscal Year 2003: ¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 2002: ¥8,200,000 (Direct Cost: ¥8,200,000)
Keywordsphoto-excited state / X-ray crystal structural analysis / synchrotron radiation / photo-induced phenomenon / transition metal complex / low-temperature vacuum X-ray camera / micro-crystal structure analysis / low-temperature structure analysis / 光誘起反応活性種 / レーザー照射 / 低温真空X線カメラ
Research Abstract

In order to reveal the photo-induced small structural changes using the single crystal structure analyses, it has been understood that the rise in heat of the crystal specimen according to the light irradiation should be a significant problem. We succeeded in the suppression of the crystal heating less than 0.1K by introducing the new timesharing IP multiple exposure method, in which incident X-ray and excitation light was intermitted synchronously by using a couple of rotary choppers.
Photo-excited structure analysis was applied to the luminescent dicopper(I) complexes [Cu_2I_2(PPh_3)_2(4,4'-bpy)]_∞, which consist of {Cu_2I_2 } planer units bridged by diimine ligands constructing infinite chain structures. Single crystal X-ray diffraction experiments under photo-illumination were performed at 40 K by using the low-temperature vacuum X-ray camera at SPring-8 BL02B1 beamline. Two set of reflection data of intensity changes owing to light irradiation were measured by the timesharing IP mu … More ltiple exposure method under two laser light of wavelengths on the absorption band (442 nm) and on its tail (532 nm). Photo-difference Fourier syntheses for the 442 nm irradiation data show significant positive and negative peaks around Cu and I atoms, though that for the 532 nm data show no significant peak. The least-squares refinement based on the photo-induced intensity changes revealed that ca. 1.1% of the Cu and I atoms moved and resulted in the shortening of the Cu-I bond and I...I distance of 0.2Å and 0.6Å, respectively.
Crystal structure analysis of the photo-induced nitrene has been determined successfully by using the host-guest complex of [(PhCH_2)_2NH_2]^+[m-C_6H_4(N_3)(COO)]^-. The intensity data were collected at 25 K using the low-temperature vacuum X-ray camera at SPring-8 before and after UV-irradiation with a high-pressure mercury lamp. It has been revealed that ca. 7% of the triplet nitrene and the isolated nitrogen molecule were generated and the C-N bond distance in the triplet nitrene was 1.34(4)Å. Less

Report

(4 results)
  • 2004 Annual Research Report   Final Research Report Summary
  • 2003 Annual Research Report
  • 2002 Annual Research Report
  • Research Products

    (28 results)

All 2005 2004 2003 2002 Other

All Journal Article (21 results) Publications (7 results)

  • [Journal Article] A Neutral Mixed-Valent Conducting Polymer Formed by Electron Transfer between Metal d and Ligand. π Orbitals2005

    • Author(s)
      M.Mitsumi
    • Journal Title

      Angew. Chem. Int. Ed. 44

      Pages: 4164-4168

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Conclusive Determination of the Absolute Stereochemistry of Chiral C_<60> Fullerene cis-3 Bis-Adducts by X-ray Crystallography and Circular Dichroism2005

    • Author(s)
      S.Kuwahara
    • Journal Title

      Angew. Chem. Int. Ed. 44

      Pages: 2-5

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] A Neutral Mixed Valent Conducting Polymer Formed by Electron Transfer between Metal d and Ligand π Orbitals.2005

    • Author(s)
      M.Mitsumi, H.Goto, S.Umebayashi, Y.Ozawa, M.Kobayashi, T.Yokoyama, H.Tanaka, S.Kuroda, K.Toriumi
    • Journal Title

      Angew.Chem.Int.Ed. 44

      Pages: 4164-4168

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Conclusive Determination of the Absolute Stereochemistry of Chiral C_<60> Fullerene cis-3 Bis-Adducts by X-ray Crystallography and Circular Dichroism2005

    • Author(s)
      S.Kuwahara, K.Obata, K.Yoshida, T.Matsumoto, N.Harada, N.Yasuda, Y.Ozawa, K.Toriumi
    • Journal Title

      Angew.Chem.Int.Ed. 44

      Pages: 2-5

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Conclusive Determination of the Absolute Configuration of Chiral C_<60>-Fullerene cis-3 Bisadducts by X-ray Crystallography and Circular Dichroism2005

    • Author(s)
      Shunsuke KUWAHARA
    • Journal Title

      Angew.Chem.Int.Ed. 44

      Pages: 2-5

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Synchrotron Radiation Structure Analyses of Photo-Excited Molecules and Photo-Induced Phenomena, and Accurate Structure Analyses of Organic-Inorganic Hybrid Compounds2005

    • Author(s)
      Koshiro TORIUMI
    • Journal Title

      SPring-8 User Experimental Report No.14(2004B)(In press)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Rational Syntheses of Linear Chain Rhodium(I)-Semiquinonato Complexes Using Redox Reaction of Rh_4(CO)_<12> Cluster with o-Benzoquinone2004

    • Author(s)
      Minoru MITSUMI
    • Journal Title

      Chem.Letters 33(8)

      Pages: 970-971

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Synchrotron Radiation Structure Analyses of Photo-Excited Molecules and Photo-Induced Phenomena, and Accurate Structure Analyses of Organic-Inorganic Hybrid Compounds2004

    • Author(s)
      Koshiro TORIUMI
    • Journal Title

      SPring-8 User Experimental Report No.13(2004A)

      Pages: 21-21

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Photoexcited Crystallography of Diplatinum Complex by Multiple-exposure IP Method2003

    • Author(s)
      Y.Ozawa
    • Journal Title

      Chem. Letters 32

      Pages: 62-63

    • NAID

      10012813210

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Structure Analysis of Photo-induced Triplet Phenylnitrene Using Synchrotron Radiation2003

    • Author(s)
      M.Kawano
    • Journal Title

      Chem. Letters 32

      Pages: 922-923

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Photoexcited Molecular Structure of Diplatinum(II) Complex by Single-Crystal X-ray Structure Analysis2003

    • Author(s)
      Y.Ozawa
    • Journal Title

      SPring-8 Research Frontiers 2001B/2002A

      Pages: 58-60

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] X線回折法による光励起分子の構造解析2003

    • Author(s)
      鳥海幸四郎
    • Journal Title

      SPring-8利用者情報誌 8

      Pages: 25-31

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Photoexcited Crystallography of Diplatinum Complex by Multiple-exposure IP Method.2003

    • Author(s)
      Y.Ozawa, M.Terashima, M.Mitsumi, K.Toriumi, N.Yasuda, H.Uekusa, Y.Ohashi
    • Journal Title

      Chem.Letters 32

      Pages: 62-63

    • NAID

      10012813210

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Structure Analysis of Photo-induced Triplet Phenylnitrene Using Synchrotron Radiation.2003

    • Author(s)
      M.Kawano, T.Takayama, H.Uekusa, Y.Ohashi, Y.Ozawa, K.Matsubara, H.Imabayashi, M.Mitsumi, K.Toriumi
    • Journal Title

      Chem.Letters 32

      Pages: 922-923

    • NAID

      10012820071

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Structure Analyses of Photo Excited Molecules by X-ray Diffraction Method. (in Japanese)2003

    • Author(s)
      K.Toriumi, Y.Ozawa
    • Journal Title

      SPring-8 Information 8(1)

      Pages: 25-31

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Photoexcited Molecular Structure of Diplatinum(II) Complex by Single-Crystal X-ray Structure Analysis.2003

    • Author(s)
      Y.Ozawa, K.Toriumi
    • Journal Title

      SPring-8 Research Frontiers 2001B/2002A

      Pages: 58-60

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Synchrotron Radiation Structure Analyses of the Light-Induced Radical Pair of a Hexaarylbiimidazolyl Derivative - Origin of the Spin Multiplicity Change2002

    • Author(s)
      M.Kawano
    • Journal Title

      Chem. Letters 2002

      Pages: 1130-1131

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] SPring-8高輝度放射光を用いた光誘起反応活性種のX線構造解析2002

    • Author(s)
      鳥海幸四郎
    • Journal Title

      Isotope News No.583

      Pages: 7-9

    • NAID

      10010432366

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Synchrotron Radiation Structure Analyses of the Light-Induced Radical Pair of a Hexaarylbiimidazolyl Derivative - Origin of the Spin Multiplicity Change.2002

    • Author(s)
      M.Kawano, Y.Ozawa, K.Matsubara, H.Imabayashi, M.Mitsumi, K.Toriumi, Y.Ohashi
    • Journal Title

      Chem.Letters 2002

      Pages: 1130-1131

    • NAID

      10010597480

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] X-ray Crystal Structure Analyses of Photo Induced Reaction Intermediates Using Intense Synchrotron Radiation. (in Japanese)2002

    • Author(s)
      K.Toriumi
    • Journal Title

      Isotope News No.583

      Pages: 7-9

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Valence-Ordering Structures and Magnetic Behavior of Metallic MMX Chain Compounds.2002

    • Author(s)
      M.Mitsumi, K.Kitamura, A.Morinaga, Y.Ozawa, M.Kobayashi, K.Toriumi, Y.Iso, H.Kitagawa, T.Mitani
    • Journal Title

      Angew.Chem.Int.Ed. 41

      Pages: 2767-2771

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Publications] Masaki KAWANO: "Structure Analysis of Photo-induced Tiplet Phenylnitrene Using Synchrotron Radiation"Chemistry Letters. 32. 922-923 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Yoshiki OZAWA: "Photoexcited Molecular Structure of Diplatinum(II) Complex by Single-Crystal X-ray Structure Analysis"SPring-8 Research Frontiers. 2001B/2002A. 58-60 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] 鳥海幸四郎: "二次元検出器の特性を生かした低分結晶解析の研究例"日本結晶学会誌. 45. 351-356 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Yoshiki OZAWA: "Photoexcited Crystallography of Diplatinum Complex by Multiple-exposure IP Method"Chemistry Letters. Vol.32,No.1. 62-63 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] Masaki KAWANO: "Synchrotron Radiation Structure Analyses of the Light-Induced Radical Pair of a Hexaarylbiimidazolyl Derivative. Origin of the Spin-Multiplicity Change"Chemistry Letters. 2002,No11. 1130-1131 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] 鳥海幸四郎: "SPring-8高輝度放射光を用いた光誘起反応活性種のX線構造解析"Isotope News. 2002年11月号. 7-9 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] 鳥海幸四郎: "X線回折法による光励起分子の構造解析"SPring-8利用者情報. Vol.8,No.1. 25-31 (2003)

    • Related Report
      2002 Annual Research Report

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Published: 2002-04-01   Modified: 2016-04-21  

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