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A Study on the structure and reactivity of encounter complex

Research Project

Project/Area Number 16205009
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionTokyo Institute of Technology

Principal Investigator

KAIZU Youkoh  Tokyo Institute of Technology, Graduate School of Science, Professor (20016140)

Co-Investigator(Kenkyū-buntansha) OTSUKA Takuhiro  Tokyo Institute of Technology, Graduate School of Science, Assistant Professor (20280993)
ASANO Motoko  Tokyo Metropolitan University, Graduate School of Science and Engineering, Associate Professor (80201888)
Project Period (FY) 2004 – 2007
Project Status Completed (Fiscal Year 2007)
Budget Amount *help
¥40,040,000 (Direct Cost: ¥30,800,000、Indirect Cost: ¥9,240,000)
Fiscal Year 2007: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000)
Fiscal Year 2006: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2005: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2004: ¥27,300,000 (Direct Cost: ¥21,000,000、Indirect Cost: ¥6,300,000)
Keywordsencounter complex / reaction of photo-excitation energy-transfer / mixed-ligand complex / ruthenium(II) and chromium(III) complexes / aqueous solution and mixed-solvent / ethanol and acetonitrile / congeniality between ligands / bipyridine and phenanthroline / 水溶液と混合溶媒 / 出会い錯体の構造 / エネルギー移動 / 水-エタノール混合溶媒 / ルテニウム(II)錯体 / クロム(III)錯体 / 光励起エネルギー移動 / 水溶液 / ドナーとアクセプター錯体 / 遭遇イオン対 / ドナーとアクセプター
Research Abstract

It has been thought that the tris-chelate metal-complexes of mixed-ligands of some poly-pyridines are completely spherical in chemical reaction in solution. However, the experimental results of energy-transfer rate-constant from the mixed-ligand Ru(II)-complex to Cr(III) complex indicate that the energy-acceptor complexes do not exist around the mixed-ligands complexes of energy-donor in encounter complex in aqueous solution. In other words, the relative geometry between the mixed-ligand Ru(II)-complex and Cr(III) complex are not isotropic but anisotropic even in encounter complex in solution. The congeniality between donor's ligand and acceptor's ligand is very important for the structure of encounter complex in aqueous solution, for example, hydrophobicity and hydrophilicity.
In mixed-solvents of water : ethanol and water : acetonitrile (v.v. 8 : 2 and 6 : 4), the relative geometry of encounter complex is different from that in aqueous solution. These results indicate that the solvent molecules of ethanol and acetonitrile affect on the relative geometry of encounter complex.
Therefore, the determination of the rate-constant of photo-excitaion energy-transfer between metal-complexes makes it possible for the structure of encounter complex in solution as molecular level.
The results in this work have a very wide application, especially in the region of chemical reaction in a living body.

Report

(5 results)
  • 2007 Annual Research Report   Final Research Report Summary
  • 2006 Annual Research Report
  • 2005 Annual Research Report
  • 2004 Annual Research Report
  • Research Products

    (34 results)

All 2008 2007 2006

All Journal Article (6 results) Presentation (28 results)

  • [Journal Article] Effect of ligand congeniality on energy transfer reaction between photo-excited tris(bipyridine)ruthenium(II) and chromate(III) complexes in aqueous solutions2006

    • Author(s)
      Otsuka, Takuhiro Iwamura, Munetaka Kaizu, Youkoh
    • Journal Title

      Inorganica Chimica Acta. 5・359

      Pages: 1351-1356

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Specific salt effects on energy transfer reactions from (Tb(2,6-pyridinedicarboxylate)3)3#8722 to Co(III)complexes in aqueous solutions2006

    • Author(s)
      Iwamura, Munetaka Morita, Makoto Otsuka, Takuhiro Kaizu, Youhoh
    • Journal Title

      Journal of Molecular Liquids. 1・128

      Pages: 71-76

    • Related Report
      2006 Annual Research Report
  • [Journal Article] An Improvement to the synthesis of deuterated meso-tetraphenylporphyrins2006

    • Author(s)
      Asano, Motoko S Abe, Hiroshi Kaizu, Youkoh
    • Journal Title

      Journal of Labelled Compounds and Radiopharmaceuticals. 7・49

      Pages: 595-602

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Intraolecular energy transfer and near-infra-red emission in a phenylene-bridged zine(II)-copper(II) porphyrin dimer2006

    • Author(s)
      Asano, Motoko S Shibuki, Masanori Kaizu, Youkoh
    • Journal Title

      Journal of Porphyrins and Phthalocyanines. 4・10

      Pages: 424-424

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Spin-multiplicity of a moderately coupled triplet#8211doublent spin pair in a biphenylene-linked porphyrin dimer2006

    • Author(s)
      Asano, Motoko S Ishizuka, Kazuhiko Kaizu, Youkoh
    • Journal Title

      Molecular Physics. 10・104

      Pages: 1609-1618

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Effect of ligand congeniality on energy transfer reaction between photo-excited tris(bipyridine)ruthenium(II) and chromate(III) complexes in aqueous solutions2006

    • Author(s)
      Takuhiro Otsuka, Munetaka Iwamura, Youkoh kaizu
    • Journal Title

      Inorganica Chimica Acta 359・5

      Pages: 1351-1356

    • Related Report
      2005 Annual Research Report
  • [Presentation] 複錯体結晶M[Ru(bpy)_3][Cr_xAl_<1-x>(ox)_3](M^+=Na^+, Li^+; 0≦X≦1)中における光励起エネルギーマイグレーション(2)2008

    • Author(s)
      石井聡、中口朋子、大塚拓洋、海津洋行
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      立教大学(東京)
    • Year and Date
      2008-03-29
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] 混合溶媒中における[Ru(bpy)_3]^<2+>とCr(III)錯体からなる遭遇イオン対の構造2008

    • Author(s)
      大木恵介、大塚拓洋、海津洋行
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      立教大学(東京)
    • Year and Date
      2008-03-29
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Annual Research Report 2007 Final Research Report Summary
  • [Presentation] 混合配位子錯体[Ru(phen)_<3-n>(bpy)_n]^<2+>(n=0〜3)の[Cr(ox)_3]^<3->錯体による消光反応2008

    • Author(s)
      鈴木健史、大木恵介、桜井美智子、大塚拓洋、海津洋行
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      立教大学(東京)
    • Year and Date
      2008-03-29
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Annual Research Report 2007 Final Research Report Summary
  • [Presentation] 非水溶媒中における輻射性イオン対のミクロな構造2008

    • Author(s)
      石原利彦、大塚拓洋、海津洋行
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      立教大学(東京)
    • Year and Date
      2008-03-29
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Annual Research Report 2007 Final Research Report Summary
  • [Presentation] Photo-excitaion energy-migration in double complex salts : M[Ru(bpy)_3][Cr_xAl_<1-x>(ox)_3] (M^+ =Na^+, Li^+ ; 0≦ X ≦1) (2)2008

    • Author(s)
      Ishii, Satoshi, Nakaguchi, Tomoko, Otsuka, Takuhiro Kaizu, Youkoh
    • Organizer
      88th Spring Conference of the chemical society of Japan
    • Place of Presentation
      at Rikkyo Univ. (Tokyo)
    • Year and Date
      2008-03-29
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] The structure of encounter complex composed of [Ru(bpy)_3]^<2+> and Cr(III) complex in mixed-solvent.2008

    • Author(s)
      Oki, Keisuke, Otsuka, Takuhiro, Kaizu, Youkoh
    • Organizer
      88th Spring Conference of the chemical society of Japan
    • Place of Presentation
      at Rikkyo Univ. (Tokyo)
    • Year and Date
      2008-03-29
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Emission quenching-reaction of mixed-ligand complex [Ru(phen)_<3-n>, (bpy)_n]^<2+> (n=0〜3) by Cr(III) complex.2008

    • Author(s)
      Suzuki, Takeshi, Oki, Keisuke, Sakurai, Michiko, Otsuka, Takuhiro, Kaizu, Youkoh
    • Organizer
      88th Spring Conference of the chemical society of Japan
    • Place of Presentation
      at Rikkyo Univ. (Tokyo)
    • Year and Date
      2008-03-29
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] The micro-structure of emissive ion pair in organic solvent.2008

    • Author(s)
      Ishihara, Toshihiko, Otsuka, Takuhiro, Kaizu, Youkoh
    • Organizer
      88th Spring Conference of the chemical society of Japan
    • Place of Presentation
      at Rikkyo Univ. (Tokyo)
    • Year and Date
      2008-03-29
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] 複錯体結晶M[Ru(bpy)_3][Cr_xAl_<1-x>(ox)_3](M^+=Na^+,Li^+;0≦X≦1)中における光励起エネルギーマイグレーション(2)2008

    • Author(s)
      石井聡、中口朋子、大塚拓洋、海津洋行
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      立教大学(東京)
    • Year and Date
      2008-03-29
    • Related Report
      2007 Annual Research Report
  • [Presentation] Energy Transfer from *[Ru(bpy)_3]^<2+>to Cr(III) Complexes in Mixed-Solvents; Water-Ethanol and Water-Acetonitrile.2007

    • Author(s)
      Keisuke Ohki, Takuhiro Otsuka, Youkoh Kaizu
    • Organizer
      Joint Conference of JMLG/EMLG Meeting 2007 and 30th Symposium on Solution Chemistry
    • Place of Presentation
      Fukuoka, Japan
    • Year and Date
      2007-11-23
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Energy transfer from ^*[Ru(bpy)_3]^<2+> to Cr(III) complexes in mixed-solvents ; water-ethanol and water-acetonitrile.2007

    • Author(s)
      Oki, Keisuke, Otsuka. Takuhiro, Kaizu, Youkoh
    • Organizer
      Joint Conference of JMLG/EMLG Meeting 2007 and 30th Symposium on Solution Chemistry
    • Place of Presentation
      at Fukuoka (in Japan)
    • Year and Date
      2007-11-23
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Energy Transfer from *[Ru(bpy)_3]^<2+> to Cr(III) complexes in Mixed-Solvents; Water-Ethanol and Water-Acetonitrile.2007

    • Author(s)
      Keisuke Ohki, Takuhiro Otsuka, Youkoh Kaizu
    • Organizer
      Joint Conference of JMLG/EMLG Meeting 2007 and 30th Symposium on Solution Chemistry
    • Place of Presentation
      Fukuoka, Japan
    • Year and Date
      2007-11-23
    • Related Report
      2007 Annual Research Report
  • [Presentation] Crystal structure and photo-excitation energy migration in crystals of double-complex salts M[Ru(bpy)_3][Cr_xAl_<1-x>(ox)_3](M^+=Na^+, Li^+; 0≦x≦1)2007

    • Author(s)
      Satoshi Ishii, Tomoko Nakaguchi, Takuhiro Otsuka, and Youkoh Kaizu
    • Organizer
      The 8th conference of the Asian Crystallographic Association
    • Place of Presentation
      Taipei, Taiwan
    • Year and Date
      2007-11-05
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Crystal structure and photo-excitation energy migration in crystals of double-complex salts M[Ru(bpy)_3][Cr_xAl_<1-x>(ox)_3] (M^+ = Na^+, Li^+ ; 0≦ x ≦1)2007

    • Author(s)
      Ishii, Satoshi, Nakaguchi, Tomoko, Otsuka, Takuhiro, Kaizu, Youkoh
    • Organizer
      The 8th Conference of the Asian Crystallographic Association
    • Place of Presentation
      at Taipei (in Taiwan)
    • Year and Date
      2007-11-05
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Crystal structure and photo-excitation energy transfer migration in crystals of double-complex salts M[Ru(bpy)_3][Cr_xAl_<1-x>(ox)_3](M^+=Na^+,Li^+;0≦x≦1)2007

    • Author(s)
      Satoshi Ishii, Tomoko Nakaguchi, Takuhiro Otsuka, and Youkoh Kaizu
    • Organizer
      The 8th Conference of the Asian Crystallographic Association
    • Place of Presentation
      Taipei, Taiwan
    • Year and Date
      2007-11-05
    • Related Report
      2007 Annual Research Report
  • [Presentation] 複錯体結晶M[Ru(bpy)_3][Cr_xAl_<1-x>(ox)_3](M^+=Na^+, Li^+; 0≦X≦1)中における光励起エネルギーマイグレーション2007

    • Author(s)
      石井聡、中口朋子、大塚拓洋、海津洋行
    • Organizer
      第57回錯体化学討論会
    • Place of Presentation
      名古屋工業大学
    • Year and Date
      2007-09-26
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] 複錯体[Cr(N-N)_3][Cr(ox)_3](N-N=en, tn,)中における光励起エネルギー移動2007

    • Author(s)
      笠原敬男、大塚拓洋、海津洋行
    • Organizer
      第57回錯体化学討論会
    • Place of Presentation
      名古屋工業大学
    • Year and Date
      2007-09-26
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Photo-excitaion energy-migration in double complex salts : M[Ru(bpy)_3][Cr_xAl_1-x(ox)_3] (M^+=Na^+, Li^+ ; 0 ≦ X≦ 1)2007

    • Author(s)
      Ishii, Satoshi, Nakaguchi, Tomoko, Otsuka, Takuhiro, Kaizu, Youkoh
    • Organizer
      58th Conference of Coordination Chemistry
    • Place of Presentation
      at Nagoya Institute of Tech.
    • Year and Date
      2007-09-26
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Photo-excitaion energy-transfer in double complex salts : [Cr(N-N)_3] [Cr(ox)_3] (N-N = en, tn)2007

    • Author(s)
      Kasahara, Takao, Otsuka, Takuhiro, Kaizu, Kaizu, Youkoh
    • Organizer
      58th Conference of Coordination Chemistry
    • Place of Presentation
      at Nagoya Institute of Tech.
    • Year and Date
      2007-09-26
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] 複錯体結晶M[Ru(bpy)_3][Cr_xAl_<1-x>(ox)_3](M^+=Na^+,Li^+;0≦X≦1)中における光励起エネルギーマイグレーション2007

    • Author(s)
      石井聡、中口朋子、大塚拓洋、海津洋行
    • Organizer
      第57回錯体化学討論会
    • Place of Presentation
      名古屋工業大学
    • Year and Date
      2007-09-26
    • Related Report
      2007 Annual Research Report
  • [Presentation] 複錯体[Cr(N-N)_3][Cr(ox)_3](N-N=en,tn,)中における光励起エネルギー移動2007

    • Author(s)
      笠原敬男、大塚拓洋、海津洋行
    • Organizer
      第57回錯体化学討論会
    • Place of Presentation
      名古屋工業大学
    • Year and Date
      2007-09-26
    • Related Report
      2007 Annual Research Report
  • [Presentation] Ru(II)錯体とCr(III)錯体からなる複錯体のアセトニトリル溶液中における発光と光励起エネルギー移動2007

    • Author(s)
      大塚拓洋、薗田新太郎、海津洋行
    • Organizer
      第20回配位化合物の光化学討論会
    • Place of Presentation
      ヴィラ舞子ホテル(兵庫県)
    • Year and Date
      2007-08-08
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Annual Research Report 2007 Final Research Report Summary
  • [Presentation] 水 アセトニトリル混合溶媒中における[Ru(bpy)_3]^<2+>からCr(III)錯体への光励起エネルギー移動2007

    • Author(s)
      大木恵介、大塚拓洋、海津洋行
    • Organizer
      第20回配位化合物の光化学討論会
    • Place of Presentation
      ヴィラ舞子ホテル(兵庫県)
    • Year and Date
      2007-08-08
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Ru(II)錯体とCr(III)錯体からなる複錯体の結晶構造と光励起エネルギー移動2007

    • Author(s)
      楊金剛、大塚拓洋、海津洋行
    • Organizer
      第20回配位化合物の光化学討論会
    • Place of Presentation
      ヴィラ舞子ホテル(兵庫県)
    • Year and Date
      2007-08-08
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Annual Research Report 2007 Final Research Report Summary
  • [Presentation] Luminescence and photo-excitation energy-transfer of double complex salts composed of Ru(II) and Cr(III) complex in acetonitrile.2007

    • Author(s)
      Otsuka, Takuhiuro, Sonoda, Shintarou, Kaizu, Youkoh
    • Organizer
      Conterence of Photo-Chemistry of 20th Coordination Compound
    • Place of Presentation
      at Vila Maiko Hotel (Hyogo)
    • Year and Date
      2007-08-08
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Photo-excitaion energy-transfer from [Ru(bpy)_3]^<2+> to Cr(III) complex in Mixed-solvent of water and acetobitrile.2007

    • Author(s)
      Oki, Keisuke ; Otsuka, Takuhiro ; Kaizu, Youkoh
    • Organizer
      20th Conference of Photo-Chemistry of Coordination Compound
    • Place of Presentation
      at Vila Maiko Hotel (Hyogo)
    • Year and Date
      2007-08-08
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Crystal structure and photo-excitaion energy-transfer in double complex salts composed of Ru(II) to Cr(III) complexes.2007

    • Author(s)
      Yang, Shingang, Otsuka, Takuhiro, Kaizu, Youkoh
    • Organizer
      20th Conference of Photo-Chemistry of Coordination Compound
    • Place of Presentation
      at Vila Maiko Hotel (Hyogo)
    • Year and Date
      2007-08-08
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] 水-アセトニトリル混合溶媒中における[Ru(bpy)_3】^<2+>からCr(III)錯体への光励起工ネルギー移動2007

    • Author(s)
      大木恵介、大塚拓洋、海津洋行
    • Organizer
      第20回配位化合物の光化学討論会
    • Place of Presentation
      ヴィラ舞子ホテル(兵庫県)
    • Year and Date
      2007-08-08
    • Related Report
      2007 Annual Research Report

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Published: 2004-04-01   Modified: 2016-04-21  

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