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Control of the assembly of pyridine sulofonate complexes and its luminescent-magnetic properties

Research Project

Project/Area Number 11440200
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionOsaka City University

Principal Investigator

KINOSHITA Isamu  Osaka City Univ., Graduate School of science, Associate professor (The present post, Professor), 大学院・理学研究科・助教授(現職教授) (80128735)

Co-Investigator(Kenkyū-buntansha) NISHIOKA Takanori  Osaka City Univ., Graduate School of Science, Lecture, 大学院・理学研究科, 講師 (10275240)
ICHIMURA Akio  Osaka City Univ., Graduate School of Science, Professor, 大学院・理学研究科, 教授 (50047396)
KARASAWA Tsutomu  Osaka City Univ., Graduate School of Science, Professor, 大学院・理学研究科, 教授 (90106336)
Project Period (FY) 1999 – 2001
Project Status Completed (Fiscal Year 2001)
Budget Amount *help
¥6,200,000 (Direct Cost: ¥6,200,000)
Fiscal Year 2001: ¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 2000: ¥3,100,000 (Direct Cost: ¥3,100,000)
KeywordsPyridine / Sulfur / Low dimensional Structure / Emission / Cu(II)-C Bond / Thiacalixpyridine / Pyridinepyridiniumthione / チアカリックス[4]ピリジン / トリポッド型配位子 / Cu(II)-炭素結合 / トリス(ピリジンチオラト)メタン / 銅錯体 / 発光特性 / Cu(I)クラスター / ピリジンスルフォナト錯体 / 複核Pd(III)錯体 / トリピリジントリスルフィド / 2,2'-ジピリジンジスルフィド / 6-メチルピリジンチオール / 2-ピリジンスルフォン酸 / 銅(I)錯体 / 異核二核錯体 / 白金(III) / クロム(III) / バナジウム(IV)
Research Abstract

After the end of the project period, we have worked on the following subject. 1)The classification and control of dimensional structure of pyridinesulfonate. 2)Development and complex formation of macrocyclic polypyridine. 3)Construction of novel Cu(II)-C(sp^3) bond using trispyridinethiomethane. 4)Exploration of luminescent phenomena of pyridinethiolato cluster of copper. Pyridinesulfonate complexes form versatile polymer structure either through covalent array or through hydrogen and p-p interaction forming 1 and 2 dimensional complex polymer. The combination of pyridine and sulfur can form interesting macrocyclic structure, thiacalix[3]pyridine. Using the ligand, we have found the first example of maclocyclic polypyridine complex. The complex of copper forms dimer structure via compensate bonding through Cu-S linkage, act as the starting material for the further coordination with various ligand. As a result, the complex exhibit interesting luminescent behavior and interaction with various aromatic systems. The C-S bond of the pyridinethiol shows interesting reactivity starting from the elimination of the elemental sulfur and forms a betain, pyridine pyridiniumthione, as a result. Following to this reaction, bis-pyridylthiomethane, and tris-pyridylthiomethane have been synthesized. The latter ligand act as a tripod ligand with pyridines and a deprotonated methane. We have found the first example of Cu(II)-C(sp^3) bond and explore the reactivity of this complex. The coordination reaction of the formation of this bond requires both Cu(I) metal source and dioxygen that suggest the existence of oxygenated deprotonation. These versatile phenomena essentially come from the compensative operation of rigid pyridine with soft and flexible sulfur.

Report

(4 results)
  • 2001 Annual Research Report   Final Research Report Summary
  • 2000 Annual Research Report
  • 1999 Annual Research Report
  • Research Products

    (20 results)

All Other

All Publications (20 results)

  • [Publications] T.S.Lobana, I.Kinoshita, K.Kimura, T.Nishioka, D.Shiomi, K.Isobe: "Pyridine-2-sulfonates as Versatile Ligands for the Synthesis of Novel Coordinative and Hydrogen-Bonded Supramolecules."Eur.J.Inorg.Chem.. 2004. 356-367 (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] I.Kinoshita, L.J.Wright, S.Kubo, K.Kimura, A.Sakata, T.Yano, R.Miyamoto, T.Nishioka, K.Isobe: "Design and Synthesis of Copper Complexes of Novel Ligands based on the Pyridinethiol Group"J.Chem.Soc.Dalton Trans.. 2003. 1993-2003 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] I.Kinoshita, A.Hamazawa, T.Nishioka, H.Adachi, H.Suzuki, Y.Miyazaki, A.Tsuboyoma, S.Okada, M.Hoshino: "Laser Photolysis Studies on CuI Complexes of Thia-calix[3]pyridine. Phosphorescence from the Intramolecular Charge-Transfer Excited State"J.Chem.Phys.Lett.. 371. 451-457 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Xie, M.Tougesaka, I.Kinoshita, K.Kanemoto, I.Akai, T.Karasawa: "Optical Properties of Hexanuclear 6-Methylpyridinethiolato-Copper(I) Crystals"Nonlinear Optics. 29. 647-653 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] R.Tanaka, T.Yano, T.Nishioka K.Nakajo, B.K.Breedlove, K.Kimura, I.Kinoshita, K.Isobe: "Thia-calix[n]pyridines, Synthesis and Coordination to Cu(I, II) ions with both N and S Donor Atoms"Chem.Commun. 2002. 1686-1687 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] T.S.Lobana, I.Kinoshita, K.Kimura, T.Nishioka, D.shiomi, K.Isobe: "Pyridine-2-sulfonates as Versatile Ligands for the Synthesis of Novel Coordinative and Hydrogen-Bonded Supramolecules"Eur.J.Inorg.Chem.. 356-367 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Kinoshita, L.J.Wright, S.Kubo, K.Kimura, A.Sakata, T.Yano, R.Miyamoto, T.Nishioka, K.Isobe: "Design and Synthesis of Copper Complexes of Novel Ligands Based on the Pyridinethiol Group"J.Chem.Soc.,Dalton Trans.. 1993-2003 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] I.Kinoshita, Y.Miyazaki, A.Tsuboyama, S.Okada, M.Hoshino: "Laser Photolysis Studies on CuI Complexes of Thia-calix[3]pyridine. Phosphorescence from the Intramolecular Charge-Transfer Excited State"Chem.Phys.Lett.. 371. 451-457 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] H.Xie, M.Tougesaka, I.Kinoshita, K.Kanemoto, I.Akai, T.Karasawa: "Optical Properties of Hexanuclear 6-Methylpyridinethiolato-Copper(I) Crystals"Nonlinear Optics. 29. 647-653 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] R.Tanaka, T.Yano, T.Nishioka, K.Nakajo, B.K.Breedlove, K.Kimura, I.Kinoshita, K.Isobe: "Thiacalix[n]pyridines, Synthesis and Coordination to Cu(I,II) ions with both N and S Donor Atoms"Chem.Commun.. 1686-1687 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Yuji Mikata: "Unprecedented Sugar-dependent in vivo Antitumor Activity of Carbohydrate-pendant cis-Diamminedichloroplatinum (II) Complexes"Bioinor. Med. Chem. Lett.. 11・23. 3045-3047 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Yuji Mikata: "Sugar Pendant Diamines"J. Org. Chem.. 66・11. 3783-3789 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] K.Nishikawa: "Synthesis and X-ray analysis of Mn-Mo mixed metal oxide cluster with cubic framework"Chemistry Letters. 2000・11. 1342-1343 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] H.Shimomura: "Formation of mu(4)-Se-2 complex by the oxidative coupling of mu-SeH complex : double-site atomic inversion of the mu(4)-Se-2 complex"Journal of Organometallic Chemistry. 611・1-2. 386-391 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] K.Kitano: "Lantern-type dinuclear Cr(III)Pt-II and V(IV)Pt-II complexes bridged by pyridine-2-thiolate. Synthesis and characterization"Journal of Chemical Society Dalton Transactions. 2000・6. 995-1000 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] 木下勇: "錯体とグリーンケミストリー"Food & Food Ingredients Journal of Japan. 186. 4-10 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] 北野健一: "Lantern-type dinuclear Cr^<III>Pt^<II> and V^<IV>Pt^<II> complexes bridged by pyridine-2-thiolate. Synthesis and Characterization"J. Chem. Soc. Dalton Trans.. 995-1000 (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] 高木秀明: "Feasible attachment of a dinuclear ruthenium complex to gold electrode surfaces. A screening method to find functional electrodes"Electrochemistry. 67. 1192-1193 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 木村健太郎: "Aerobic oxidation of a disulfide to its sulfonate leading to supramolecular pyridine-2-sulfonato Cu(II) and Zn(II) complexes"Chem. Commun.. 497-498 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 高良 聡: "Direct observation by electrospray ionization mass spectrometry of [Cp^*RhMo_3O_8(OMe)_5]^-, a key intermediate in the formation of the double-bookshelf-type oxide cluster [(Cp^*Rh)_2Mo_6O_20(OMe)_2]^<2->"Angew. Chem. Int. ed. Engl.. 38. 3051-3053 (1999)

    • Related Report
      1999 Annual Research Report

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Published: 2000-04-01   Modified: 2016-04-21  

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