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Determination of Ground State Spin Multiplicity of Basic non-Kekule Hydrocarbons by Measuring Paramagnetic Susceptibility.

Research Project

Project/Area Number 06453035
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field Organic chemistry
Research InstitutionKYUSHU UNIVERSITY

Principal Investigator

IWAMURA Hiizu  IFOC,Kyushu University, Professor, 有機化学基礎研究センター, 教授 (10011496)

Co-Investigator(Kenkyū-buntansha) MATSUDA Keji  IFOC,Kyushu University, Research Associate, 有機化学基礎研究センター, 助手 (80262145)
Project Period (FY) 1994 – 1995
Project Status Completed (Fiscal Year 1995)
Budget Amount *help
¥7,000,000 (Direct Cost: ¥7,000,000)
Fiscal Year 1995: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 1994: ¥5,400,000 (Direct Cost: ¥5,400,000)
Keywordsdiradical / non-Kekule molecules / tetramethleneethane / matrix isolation / triplet ground state
Research Abstract

2,3-Dimethylenecyclohexa-1,4-diyl (1) is a disjoint diradical and the ground-state multiplicity is still in controversy. By means of ESR spectroscopy and magnetic measurement, the ground-state multiplicity of the title compound was studied. From orthophtalic acid, 5,6-dimethylene-2,3-diazabicyclo[2,2,2, ]oct-2-ene was synthesized according to the method of W.R.Roth. The photolysis was carried out in MTHF matrix by using light from high-pressure mercury lamp to give 1. The photoproduct depended on the wavelenght of irradiation. The light of 312.6 nm gave the target molecule and the light of 302.2 nm gave another product. The magnetic property of 1 was investigated by means of direct measurement of the magnetization. It was found that the singlet and triplet state of 1 was almost degenerate. This result is a crucial determination of the problem where there has been a long controversy between theory and experiment.

Report

(3 results)
  • 1995 Annual Research Report   Final Research Report Summary
  • 1994 Annual Research Report
  • Research Products

    (24 results)

All Other

All Publications (24 results)

  • [Publications] Katsuya Inoue: "Assemblage and Alignment of the Spins of the Organic Trinitroxide Radical with a Quintet Ground State by Means of Complexation with Magnetic Megnetic Metal lons.A Molecule-Based Magnet whth Three-Dimensional Structure and High TC of 46K" J.Am.Chem.Soc.118(7). 1803-1804 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Hiizu Iwamura: "High-Spin Polynitroxide Radicals as Versatile Bridging Ligands for Transition Metal Complexes with High Ferri-Ferromagnetic TC." Pure Appl.Chem.68(2). 243-252 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Noboru Koga: "Diazodi (4-pyridyl) methane as a Photo-responsive Spin Source/Magnetic Coupling Unit." Angew.chem,Int.Ed,Engl.35(7). 755-757 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Katsuya Inoue: "Spontaneous Magnetization in a 2 : 3 Complex Formed by 3,4′,5-Tris (N-oxy-tert-butylamino) biphenyl and Manganese (II) Bis (hexafluoroacetylacetonate)." Adv.Mater. 8(1). 73-76 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Daniela C.Oniciu: "Synthesis and EPR Characterisation of Triphenylmethane Derivatives Carrying N-tert-Butyl Nitroxide Radical Moieties : Use of the Diradicalas a Ligand for a Complex with MnII (hfac) 2." J.Chem.Soc.,Perkin Trans.2. 907-913 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Junpei Fujita: "Antiferromagnetic Exchange Interaction among the Three Spins Placed in an Isosceles Triangular Configuration in 2,4-Dimethoxy-1,3,5-benzenetriyltris (N-tert-butyl nitroxide)." J.Am.Chem.Soc.118(39). 9347-9351 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Kenji Matsuda: "Molecule Based Magnetic Materials.Theory,Techniques,and Applications" American Chemical Society(共同執筆), 15 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K.Inoue, T.Hayamizu.H.Iwamura, Daisuke Hashizume, and Yuji Ohashi: "Assemblage and Alignment of the Spins of the Organic Trinitroxide Radical with a Quintet Ground State by Means of Complexation with Magnetic Metal lons. A Molecule-Based Magnet with Three-Dimensional Structure and High T_C of 46K." J.Am.Chem.Soc.118, (7). 1803-1804 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] H.Iwamura, K.Inoue, and T.Hayamizu: "High-Spin Polynitroxide Radicals as Versatile Bridging Ligands for Transition Metal Complexes with High Ferri-/Ferromagnetic T_C." Pure Appl.Chem.68, (2). 243-252 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] N.Koga, Y.Ishimaru, and H.Iwamura: "Diazodi (4-pyridyl) methane as a Photo-responsive Spin Source/Magnetic Coupling Unit." Angew.Chem.Int.Ed.Engl.35, (7). 755-757 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K.Inoue and H.Iwamura: "Spontaneous Magnetization in a 2 : 3 Complex Formed by 3,4', 5-Tris (N-oxy-tertbutylamino) biphenyl and Manganese (II) Bis (hexafluoroacetylacetonate)." Adv.Mater.8.(1). 73-76 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Daniela C.Oniciu, K.Matsuda, and H.Iwamura: "Synthesis and EPR Characterisation of Triphenylmethane Derivatives Carrying N-tert-Butyl Nitroxide Radical Moieties : Use of the Diradicalas a Ligand for a Complex with Mnll (hfac)_2." J.Chem.Soc., Perkin 2.1996. 907-913 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Junpei Fujita, Masakazu Tanaka, Hiroshi Suemune, Noboru Koga, Kenji Matsuda, and Hiizu Iwamura: "Antiferromagnetic Exchange Interaction among the Three Spins Placed in an Isosceles Triangular Configuration in 2,4-Dimethoxy-1,3,5-benzenetriyltris (N-tert-butyl nitroxide)." J.Am Chem.Soc.118, (39). 9347-9351 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K.Matsuda, N.Nakamura, Kazuyuki Takahashi, K.Inoue, N.Koga, and H.Iwamura: Design, Synthesis, and Characterization of p-Cross-Conjugated Polycarbenes with High-Spin Ground States. M.M.Turnbull, T.Sugimoto, and L,K.Thompson, eds., ACS Symposium Series 644, "Molecule-Based Magnetic Materials. Theory, Techniques, and Applications". ACS Washington, D.C, 142-156 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K. Matsuda: "Effect of the Oxidation State of the Sulfur Atom on the Exchange Interaction between Two Triplet Carbene Units through Diphenyl Sulfide p, p′-Diyl Couplers" Chem. Lett.1995. 1085-1086 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] K. Matsuda: "Design and Synthesis of a “Starburst" - Type Nonadiazo Compound and Magnetic Characterization of its Photoproduct"" Chem. Eur. J.2. 259-263 (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] D. C. Oniciu: "Synthesis and ESR Characterization of Triphenylmethane Derivatives Carrying N-tert-Butyl Nitroxide Radical Moieties: Use of the Diradical as a Ligand for a Complex with Mn(II)(hfac_2)" J. Chem. Soc. Perkin Trans. 2. (in press). (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] K. Matsuda: "Synthesis and ESR Characterisation of [3-(N-Oxy-t-butylamino)-5-t-butylphenyl]phenylcarbene with a Quartet Ground State" J. Chim. Soc., Chem. Comm.(in press. ). (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] K. Matsuda: "Design,Synthesis,and Characterization of Three Kinds of π-Cross-Conjugated Hexacarbenes with High-Spin(S=6)Ground States"" J. Am. Chem. Soc.117. 5550-5560 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Kenji Matsuda: "Exploratory and Mechanistic Studies of the Trimerization Reaction of Benzoylacetylenes in the Presence of a Secondary amine" Chem.Lett.1994. 1765-1768 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Kenji Matsuda: "Photochemical Production of Highly Ordered Spins in Organic Solids" Mol.Cryst.Liq.Cryst.253. 33-40 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Masaki Noro: "Carbene-Carbene Interconversion between 1-and 3-Phenyl-2-propynylidenes" J.Am.Chem.Soc.116. 6179-6190 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Weston Thatcher Borden: "Violations of Hund's Rule in Non-Kekule Hydrocarbons:Theoretical Prediction and Experimental Verification" Acc.Chem.Res.27. 109-116 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Hiizu Iwamura: "Acetylenic Compounds as Building Blocks for High-Spin Molecules and Molecular Assembies" P.J.Stang and F.Diedrich(in press),

    • Related Report
      1994 Annual Research Report

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Published: 1994-04-01   Modified: 2016-04-21  

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