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2001 Fiscal Year Final Research Report Summary

Creation of solid-state functionalities using bimolecules.

Research Project

Project/Area Number 11640559
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionUniversity of Tsukuba (2000-2001)
Japan Advanced Institute of Science and Technology (1999)

Principal Investigator

KITAGAWA Hiroshi  University of Tsukuba chemistry Associate Professor, 化学系, 助教授 (90234244)

Project Period (FY) 1999 – 2000
KeywordsHydrogen bond / Molecular conductor / Charge transfer complex / Mixed-valence state / M-I transition / Electron-proton cooperation
Research Abstract

We have focused on a one-dimensional metal-dimer system with dynamical spin-charge-lattice coupling, exhibiting many kinds of charge-ordered states associated with metal-insulator transitions. In this paper, we present on an MMX-chain system in which there exists J-D…-I-M-M-I-… chains. Some of me possible 1-D structural modes for the MMX chain are shown below.
We have focused on a one-dimensional metal-dimer system with dynamical spin-charge-lattice coupling, exhibiting many kinds of charge-ordered states associated with metal-insulator transitions. In this paper, we present on an MMX-chain system in which there exists J-D…-I-M-M-I-… chains. Some of me possible 1-D structural modes for the MMX chain are shown below.
(1) ---M2.5+-M2.5+―X―M2.5+-M2.5+―X―M2.5+-M2.5+―X---
(2) ---M2+-M2―X-M3+-M3+-X―M2+-M2+―X-M3+-M3+-X---
(3) ---M2+-M3+-X―M2+-M3+-X―M2+-M3+-X―M2+-M3+-X---
(4) ---M2+-M3+-X-M3+-M2+―X―M2+-M3+-X-M3+-M2+―X---
According to our recent work, the Ni2(MeCS2)4I salt was found to exhibit a fiel … More d-induced phase transition accompanying a spin transition between a 1-D Heisenberg AF magnetic spin system with J〜-50 K (a-phase) and Curie spin system with J〜0 K (p-phase). In order to investigate two different spin states, several physical measurements were carried out on Ni2(MeCS2)4I.
It exhibits a semiconducting behavior, which is consistent with a Mott-Hubbard insulator. The XPS spectra shows a trapped-valence state of +II and +III. Each phase is considered to have the 1-D structural mode of -I―Ni2+-Ni3+-I-Ni3+-Ni2+―I―Ni2.5+-Ni2.5―I-, which was confirmed by Raman, IR, UV-VIS-NIR spectra and magnetic susceptibility.
At 2 K, if the magnetic field of 5 T is applied, the a-phase is transformed to the p-phase, which can be obtained as a metastable state even at room temperature and zero-field. On the other hand, if the magnetic field of 5 T is applied at 300 K, the P-phase is reversibly transformed to the a-phase. This field-induced phenomenon is considered to be derived from an orbital degree of freedom, resulting the field-induced orbital ordering. Detailed investigations are in progress. Less

  • Research Products

    (14 results)

All Other

All Publications (14 results)

  • [Publications] R.Makiura et al.: "Electronic State of a Halogen-Bridged Mixed-Valence Binuclear Complex, Ni_2(dta)_4I"Molecular Crystals & Liquid Crystals. (in press).

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Mitsumi et al.: "Novel Valence-Ordering Structures and Magnetic Behavior of New Metallic MMX Chain Compounds"Angewandte Chemie International Edition. (in press).

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  • [Publications] M.Mitsumi et al.: "Structural Phase Transition and Valence Fluctuation Observed in New MMX Chain Compound, Pt_2(n-PrCS_2)_4I"Chemistry Letters. 258-259 (2002)

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  • [Publications] T.Kawashima et al.: "Syntheses and Physical Properties of Quasi-One-Dimensional Halogen-Bridged Cu^<II>-Pt^<IV> Mixed-Metal Complexes [Cu(chxn)_2][PtX_2(Chxn)_2]X_4"Inorganic Chemistry. 40. 6651-6655 (2001)

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  • [Publications] M.Mitsumi et al.: "Metallic Behavior and Periodical Valence Ordering in a MMX Chain Compound"Journal of the American Chemical Society. 123. 11179-11192 (2001)

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  • [Publications] Y.Miyazaki et al.: "Heat Capacity of the Halogen-Bridged Mixed-Valence Complex Pt_2(dta)_4I"Journal of the Physical Chemistry B. 106. 192-202 (2001)

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  • [Publications] T. Kawashima, S. Miya, T. Manabe, M. Yamashita, K. Takizawa, T. Ishii, H. Matsuzaka, T. Sonoyama, H. Kitagawa, T. Mitani. H. Matsuzaki, H. Kishida, H. Okamoto, R. Ikeda: "Charge Fluctuation in Quasi-One-Dimensional Halogen-Bridged Platinum Binuclear Mixed-Valence Compounds, A4 [Pt2(pop)4I]・nH2O"Mol. Cryst. Liq. Cryst.. 342. 145-150 (2000)

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  • [Publications] R. Makiura, I. Nagasawa, N. Kimura, S. Ishimaru, H. Kitagawa, R. Ikeda: "An Unusual Six-Co-Ordinate Platinum(II) Complex Containing A Neutral 12 ligand"Chem. Commun.. 17. 1642-1643 (2001)

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  • [Publications] M. Mitsumi, T. Murase, H. Kishida, T. Yoshinari, Y. Ozawa, K. Toriumi, T. Sonoyama, H. Kitagawa, T. Mitani: "Metallic Behavior and Periodical Valence-Ordering in a MMX Chain Compound, Pt(EtCS2)4I"J. Am. Chem. Soc.. 123. 11179-11192 (2001)

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  • [Publications] T. Kawashima, K. Takai, H. Aso, T. Manabe, H. Miyasaka, H. Matsuzaka, M. Yamashita, H. Okamoto, H. Kitagawa, M. Shiro, K. Toriumi: "Syntheses and Physical Properties of Quasi-One-Dimensional Halogen-Bridged CuIIPtlV Mixed-Metal Complexes, [ Cu(chxn)2][PtX2(chxn)2]X4"Inorg. Chem.. 40. 6651-6655 (2001)

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  • [Publications] S. Maki, Y. Morita, H. Kitagawa, T. Mitani, K. Nakasuji: "A Novel Charge-Transfer Complex of TTF Having Uracil Moiety with TCNQ"Synth. Met.. 120. 741-742 (2001)

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  • [Publications] M. Fujishima, S. Kanda, T. Mitani, H. Kitagawa: "Hydrogen-Induced Properties of Copper Coordination Polymer: catena-fi-NJV-bis-(hydroxyethyl) dithiooxamidatocopper(II)"Synth. Met.. 119. 485-486 (2001)

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  • [Publications] H. Kitagawa, S. Nakagami, T. Mitani: "Low-Temperature X-Ray Single-Crystal Analysis of a Conductive Mixed-Valence MMX-Chain System, Pt2(dta)4I (dta=CH3CS2-)"Synth. Met.. 116. 401-404 (2001)

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  • [Publications] T. Manabe, T. Kawashima, T. Ishii, H. Matsuzaka, M. Yamashita, K. Marumoto, H. Tanaka, S. Kuroda, H. Kitagawa, T. Mitani, H. Okamoto: "Syntheses and Physical Properties of Quasi-One-Dimensional Chloro-Bridged Ni-Pd Mixed-Metal MX-Chain Compounds, Nil-xPdx(chxn)2C13"Synth. Met.. 116. 415-418 (2001)

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Published: 2003-09-17  

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