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2004 Fiscal Year Final Research Report Summary

Study on the construction of photoresponsive single-molecule magnets in frozen solutions

Research Project

Project/Area Number 14204071
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Research Field 機能・物性・材料
Research InstitutionKYUSHU UNIVERSITY

Principal Investigator

KOGA Noboru  Kyushu University, Graduate School of Pharmaceutical Sciences, Professor, 大学院・薬学研究院, 教授 (60161890)

Co-Investigator(Kenkyū-buntansha) KARASAWA Satoru  Kyushu University, Graduate School of Pharmaceutical Sciences, Research Associate, 大学院・薬学研究院, 助手 (80315100)
AKITA Takeyuki  Kyushu University, Graduate School of Pharmaceutical Sciences, Research Associate, 大学院・薬学研究院, 助手 (50294963)
Project Period (FY) 2002 – 2004
KeywordsSingle-molecule Magnet / Hysteresis / Carbene / Quantum Tunneling Effect / Cobalt Complexes / Ac Magnetic susceptibility
Research Abstract

For the construction of monometallic single-molecule magnets (SMMs), We proposed to use the heterospin systems consisting of the 2p organic spins and the 3d metal ions. In our heterospin systems, pyridine ligands carrying mono-, di-, and tricarbene (S=2/2,4/2, and 6/2, respectively) and high-spin Co(II) ions, CoCl_2 and Co(p-tolsal)_2, were employed as the 2p organic spins and the 3d metal ions, respectively. Various combinations of two components, diazo-pyridine ligands and Co(II) ions, in solutions were mixed in appropriate ratios. To avoid the intermolecular magnetic interaction, the frozen solution conditions were used as the samples for SQUID measurements. The ac and dc magnetic susceptibility measurements for six samples of the complexes were carried out before and after irradiation. In ac magnetic susceptibility measurements after irradiation of six samples, the in-phase and out-of phase components (χ' and χ", respectively) with the applying frequency dependence were observed, indicating that the cobalt complexes have slow magnetic relaxations. The values of the activation barriers, U_<eff>, for flipping the spin were estimated to be 40- 93 K for the six complexes. In the dc field dependence of magnetization at 1.9 K, relatively large hysteresis loops with coercive force, H_c=7-10 kOe for the six complexes were observed. Obtained values of U_<eff>, τ_0, and H_c, for all six complexes were summarized together with those for the related complexes. In this work, we successfully prepared the monometallic single-molecule magnets in frozen solution. Furthermore, by changing the S values of the complexes systematically, it was concluded that the activation barrier, U_<eff>, for flipping the spin and the relaxation time due to the resonant quantum tunneling effect increased and decreased, respectively, with increasing S value of the complex.

  • Research Products

    (23 results)

All 2005 2004 2003 2002

All Journal Article (21 results) Book (2 results)

  • [Journal Article] Synthesis and EPR studies of 2-N-tert-butylaminoxylpurin derivatives2005

    • Author(s)
      T.Kaneko, M.Aso, N.Koga, H.Suemune
    • Journal Title

      Org.Lett. 7

      Pages: 303-305

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Molecule-Based Magnets in Heterospin Systems2005

    • Author(s)
      N.Koga, S.Karasawa
    • Journal Title

      Bull.Chem.Soc.Jpn. (In press)

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] CRYSTAL STRUCTURES AND MAGNETIC PROPERTIES OF COMPLEXES OF M(NO_3)_2 ; M=Mn^<II>, Co^<II>, Ni^<II>, AND Cu^<II>, WITH PYRIDINE LIGANDS CARRYING AN AMINOXYL RADICAL2005

    • Author(s)
      Z.Zhu, S.Karasawa, N.Koga
    • Journal Title

      Polyhedron (In press)

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Magnetic properties of dendritic polycarbenes substituted by bulky peripheral groups2005

    • Author(s)
      T.Akita, N.Koga
    • Journal Title

      Polyhedron (In press)

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Molecule-Based Magnets in Heterospin Systems2005

    • Author(s)
      N.Koga, S.Karasawa
    • Journal Title

      Bull.Chem.Soc.Jpn. (in press)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] CRYSTAL STRUCTURES AND MAGNETIC PROPERTIES OF COMPLEXES OF M(NO_3)_2; M=Mn^<II>, Co^<II>, Ni^<II>, AND Cu^<II>, WITH PYRIDINE LIGANDS CARRYING AN AMINOXYL RADICAL2005

    • Author(s)
      Z.Zhu, S.Karasawa, N.Koga
    • Journal Title

      Polyhedron (in press)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Magnetic properties of dendritic polycarbenes substituted by bulky peripheral groups2005

    • Author(s)
      T.Akita, N.Koga
    • Journal Title

      Polyhedron (in press)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Magnetic Behavior of Tetrakis[4-(N-tert-butyl-N-oxylamino)pyridine]bis(isocyanato-N)cobalt(II) in Frozen Solution2004

    • Author(s)
      S.Kanegawa, S.Karasawa, M.Nakano, N.Koga
    • Journal Title

      J.Chem.Soc.Chem.Comm.

      Pages: 1750-1751

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Magnetic Behavior of Tetrakis[4-(N-tert-butyl-N-oxylamino)pyridine]bis(isocyanato-N)cobalt(II) in Frozen Solution2004

    • Author(s)
      S.Kanegawa, S.Karasawa, M.Nakano, N.Koga
    • Journal Title

      J.hem.Soc.Chem.Comm.

      Pages: 1750-1751

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Magnetic Property after Irradiation of Tetrakis[4-(α-diazobenzyl)-pyridine]copper(II) in a Frozen Solution2003

    • Author(s)
      H.Morikawa, S.Karasawa, N.Koga
    • Journal Title

      Appl.Magn.Reson. 23

      Pages: 507-515

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] On the g Value Shift and Intersystem Crossing in Photo-Excited Radical-Triplet Systems2003

    • Author(s)
      Y.Iwasaki, K.Katano, Y.Ohba, S.Karasawa, N.Koga, S.Yamauchi
    • Journal Title

      Appl.Magn.Reson. 23

      Pages: 377-391

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] A simple and efficient method for synthesis of 5-substituted 2'-deoxyuridine nucleosides using metal-halogen exchange reaction of 5-iodo-2'-deoxyuridine sodium salt2003

    • Author(s)
      M.Aso, T.Kaneko, M.Nakamura, N.Koga, H.Suemune
    • Journal Title

      J.Chem.Soc.Chem.Commun.

      Pages: 1094-1095

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Magnetic behaviors after irradiation of assemblies consisting of bis(hexafluoroacetylacetonato)copper(II) and tetrapyridyl-pentadiazo compounds in frozen solutions2003

    • Author(s)
      S.Karasawa, N.Koga
    • Journal Title

      Polyhedron 22

      Pages: 1877-1882

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Magnetic Properties of Tetrakis[4-(a-diazobenzyl)pyridine]-bis(thiocyanato-N)cobalt(II) in Frozen Solution after Irradiation. Formation of a Single-molecule Magnet in Frozen Solution2003

    • Author(s)
      S.Karasawa, G.Zhou, H.Morikawa, N.Koga
    • Journal Title

      J.Am.Chem.Soc. 125

      Pages: 13676-13677

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Magnetic Property after Irradiation of Tetrakis[4-(α-diazobenzyl) pyridinel]copper(II) in a Frozen Solution2003

    • Author(s)
      H.Morikawa, S.Karasawa, N.Koga
    • Journal Title

      Appl.Magn.Reson. 23

      Pages: 507-515

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] On the g Value Shift and Intersystem Crossing in Photo-Excited Radical-Triplet Systems.2003

    • Author(s)
      Y.Iwasaki, K.Katano, Y.Ohba, S.Karasawa, N.Koga, S.Yamauchi
    • Journal Title

      Appl.Magn.Reson. 23

      Pages: 377-391

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] A simple and efficient method for synthesis of 5-substituted 2'-deoxyuridine nucleosides using metal-halogen exchange reaction of 5-iodo-2'-deoxyuridine sodium salt2003

    • Author(s)
      M.Aso, T.Kaneko, M Nakamura, N.Koga, H.Semune
    • Journal Title

      J.Chem.Soc.Chem.Commun.

      Pages: 1094-1095

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Magnetic Properties of Tetrakis[4-(α-diazobenzyl)pyridine]-bis(thiocyanato-N)cobalt (II) in Frozen Solution after Irradiation. Formation of a Single-molecule Magnet in Frozen Solution.2003

    • Author(s)
      S.Karasawa, G.Zhou, H.Morikawa, N.Koga
    • Journal Title

      J.Am.Chem.Soc. 125

      Pages: 13676-13677

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Theoretical Studies of Magnetic Interactions in Mn(II)(hfac)2{di-(4-pyridyl)phenylcarbene} and Cu(II)(hfac)2{di-(4-pyridyl)phenylcarbene}2002

    • Author(s)
      Y.Takano, Y.Kitagawa, T.Onishi, Y.Yoshioka, K.Yamaguchi, N.Koga, H.Iwamura
    • Journal Title

      J.Am.Chem.Soc. 124

      Pages: 450-461

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Theoretical Study on the Exchange Interaction between Metal Ion and Organic Radical through Pyridine, Bipyridine, and Terpyridine Ligands2002

    • Author(s)
      J.-P.Zhang, M.Suehiro, A.Sakane, S.Karasawa, T.Akita, N.Koga
    • Journal Title

      Mol.Cryst.Liq.Cryst. 376

      Pages: 431-436

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Theoretical Studies of Magnetic Interactions in Mn(II)(hfac)_2 {di-(4-pyridyl)phenylcarbene} and Cu(II)(hfac)_2{di-(4-pyridyl) phenylcarbene}2002

    • Author(s)
      Y.Takano, Y.Kitagawa, T.Onishi, Y.Yoshioka, K.Yamaguchi, N.Koga, H.Iwamura
    • Journal Title

      J.Am.Chem.Soc. 124

      Pages: 450-461

    • Description
      「研究成果報告書概要(欧文)」より
  • [Book] From High-spin Polycarbenes to Carbene-based Magnets in Carbene Chemistry : from Fleeting Intermediates to Powerful Reagents2002

    • Author(s)
      N.Koga, H.Iwamura
    • Total Pages
      22
    • Publisher
      FontisMedia S.A.
    • Description
      「研究成果報告書概要(和文)」より
  • [Book] From High-spin Polycarbenes to Carbene-based Magnets, Carbene Chemistry: from Fleeting Intermediates to Powerful Reagents, Chapter 92002

    • Author(s)
      N.Koga, H.Iwamura
    • Total Pages
      271-293
    • Publisher
      FontisMedia SA
    • Description
      「研究成果報告書概要(欧文)」より

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Published: 2006-07-11  

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