2002 Fiscal Year Annual Research Report

動的なスピン・電荷・格子結合を有する金属錯体の創製と磁場による軌道秩序形成

Research Project

Project/Area Number	14340215
Research Institution	University of Tsukuba
Principal Investigator	北川宏筑波大学, 化学系, 助教授 (90234244)
Co-Investigator(Kenkyū-buntansha)	池田龍一筑波大学, 化学系, 教授 (90022631)
Keywords	混合原子価 / 磁場誘起相転移 / MMX-chain / スピン / 電荷秩序 / 軌道秩序
Research Abstract	電解合成により、ダイレクトチェイン構造を有する(架橋配位子の無い)物質系[Pt_2(dta)_4]A(A=CIO_4-,BF_4-,AsF_6-,HSO_4-など)の開発を行った。また、価数揺動制御のため二種類の二座配位子を用いた、Pt^<II>Pt^<II>(A)_4とPt^<III>Pt^<III>(B)_4をユニットとした系の構築も試みた。合成した試料の構造評価は、単結晶X線構造解析にて行った。基礎光学定数を求めるため、単結晶を用いて、赤外から可視,紫外域にいたる偏光顕微反射スペクトルを測定し、電気伝導性錯体の基礎物性パラメーター(キャリアー数、移動度、光学伝導度など)を明らかにした。また所有する顕微用クライオスタットにより4.2Kまでの光学スペクトルの温度依存性を調べた。クラマス-クロニッヒ(K-K)変換により解析を行い、それらの電子構造と電荷移動励起状態の性質を解明した。さらにNi_2(dta)_4lにおける磁場誘起相転移現象の解明には、申請者が併任する北陸先端科技大の磁場システム(12T,1.8-300K)を用いて、強磁場下における光磁気特性を調べ、スピンとの結合状態についての詳細な知見を得た。さらには磁場による物性のコントロールも試みる予定である

Research Products

(16 results)

All Other

All Publications (16 results)

[Publications] Y.Miyazaki, Qi Wang, A.Sato, K.Saito, M.Yamamoto, H.Kitagawa, T.Mitani, M.Sorai: "Heat Capacity of the Halogen-Bridged Mixed-Valence Complex Pt_2(dta)_4I (dta=CH_3CS_2)"J.Phys.Chem.. 106. 197-202 (2002)
[Publications] M.Mitsumi, S.Umebayashi, Y.Ozawa, K.Toriumi, H.Kitagawa, T.Mitani: "Structural Phase Transition and Valence Fluctuation Observed in a New MMX Chain Compound, Pt_2(n-PrCS_2)_4I"Chemistry Letters. 258-259 (2002)
[Publications] Y.Nagao, M.Fujishima, R.Ikeda, S.Kanda, H.Kitagawa: "Highly Proton-Conductive Copper Coordination Polymers"Synthetic Metals. (in press).
[Publications] M.Fujishima, Y.Nagao, R.Ikeda, S.Kanda, H.Kitagawa: "Substituent Effect on e Magnetic Properties of Copper Coordination Polymers with Dithiooxamide and N, N'-bis-(hydroxyethyl)dithiooxamide"Synthetic Metals. (in press).
[Publications] M.Ohmoto, S.Maki, Y.Morita, T.Kubo, H.Kitagawa, T.Okubo, T.Mitani, K.Nakasuji: "Complementary Double Hydrogen-Bonded CT Complexes of TTF Having Uracil Moiety"Synthetic Metals. (in press).
[Publications] M.Fujishima, R.Ikeda, S.Kanda, H.Kitagawa: "Electronic State of A Hydrogen-Doped Copper Coordination Polymer : catena-μ-N, N'-bis-(hydroxyethyl)dithiooxamidatocopper(II),(HOC_2H_4)_2dtoaCu"Mol.Cryst.Liq.Cryst.. 379. 223-228 (2002)
[Publications] Y.Nagao, R.Ikeda, S.Kanda, H.Kitagawa: "Complex-Plane Impedance Study on A Hydrogen-Doped Copper Coordination Polymer : N, N'-bis-(2-hydroxy-ethyl)dithiooxamidatocopper(II)"Mol.Cryst.Liq.Cryst.. 379. 89-94 (2002)
[Publications] A.Kobayashi, H.Kitagawa, R.Ikeda: "Structural and Optical Properties of Pt_2(dtp)_4Br_2 (dtp = dithiopropionato) and Its Halogen-Replacement Effect"Mol.Cryst.Liq.Cryst.. 379. 315-320 (2002)
[Publications] S.Takaishi, H.Kitagawa, R.Ikeda: "Relaxation Process of CT Exciton State in a One-Dimensional MX-Chain Compound 〔NiBr(chxn〕_2]Br^2"Mol.Cryst.Liq.Cryst.. 379. 279-284 (2002)
[Publications] R.Makiura, H.Kitagawa, R.Ikeda: "Electronic State of A Halogen-Bridged Mixed-Valence Binuclear Complex, Ni_2(dta)_4I"Mol.Cryst.Liq.Cryst.. 379. 309-314 (2002)
[Publications] M.Mitsumi, K.Kitamura, A.Morinaga, Y.Ozawa, M.Kobayashi, K.Toriumi, Y.Iso, H.Kitagawa, T.Mitani: "Novel Valence-Ordering Structures and Magnetic behavior of New Metallic MMX Chain Compounds"Angrew.Chem.Int.Ed.. 41. 2767-2771 (2002)
[Publications] Y.Morita, S.Maki, M.Ohmoto, H.Kitagawa, T.Okubo, T.Mitani, K.Nakasuji: "Hydrogen-Bonded Charge-Transfer Complexes of TTF Containing a Uracil Moiety : Crystal Structures and Electronic Properties of the Hydrogen Cyananilate and TCNQ Complexes"Organic Letters. 4. 2185-2188 (2002)
[Publications] G.Saito, H.Sasaki, T.Aoki, Y.Yoshida, A.Otsuka, H.Yamochi, O.Drozdova, K.Yakushi, H.Kitagawa: "Complex Formation of Ethylenedioxyethylenedithiotetrathiafulvalene (EDOEDT-TTF : EOET) and its self-assembling ability"J.Mater.Chem.. 12. 1640-1649 (2002)
[Publications] S.Takaishi, M.Kano, H.Kitagawa, Y.Furukawa, K.Kumagai, R.Ikeda: "Spin Structure and Dynamics in a Spin 1/2 One Dimensional Antiferromagnet, [NiBr(chxn)_2]Br_2"Chem.Lett. 856-857 (2002)
[Publications] H.Kitagawa, Y.Nagao, M.Fujishima, R.Ikeda, S.Kanda: "Highly Proton-Conductive Copper Coordination Polymer, H_2dtoaCu"Inorg.Chem.Commun.. 6. 346-348 (2003)
[Publications] M.Yamauchi, Y.Isobe, R.Ikeda, H.Kitagawa: "A Study on Hydrogen Adsorption of Polymer-Protected Pt Nanoparticles"Synth.Met.. (in press).

2002 Fiscal Year Annual Research Report

動的なスピン・電荷・格子結合を有する金属錯体の創製と磁場による軌道秩序形成

Principal Investigator

北川 宏 筑波大学, 化学系, 助教授 (90234244)

Research Products

[Publications] Y.Miyazaki, Qi Wang, A.Sato, K.Saito, M.Yamamoto, H.Kitagawa, T.Mitani, M.Sorai: "Heat Capacity of the Halogen-Bridged Mixed-Valence Complex Pt_2(dta)_4I (dta=CH_3CS_2)"J.Phys.Chem.. 106. 197-202 (2002)

[Publications] M.Mitsumi, S.Umebayashi, Y.Ozawa, K.Toriumi, H.Kitagawa, T.Mitani: "Structural Phase Transition and Valence Fluctuation Observed in a New MMX Chain Compound, Pt_2(n-PrCS_2)_4I"Chemistry Letters. 258-259 (2002)

[Publications] Y.Nagao, M.Fujishima, R.Ikeda, S.Kanda, H.Kitagawa: "Highly Proton-Conductive Copper Coordination Polymers"Synthetic Metals. (in press).

[Publications] M.Fujishima, Y.Nagao, R.Ikeda, S.Kanda, H.Kitagawa: "Substituent Effect on e Magnetic Properties of Copper Coordination Polymers with Dithiooxamide and N, N'-bis-(hydroxyethyl)dithiooxamide"Synthetic Metals. (in press).

[Publications] M.Ohmoto, S.Maki, Y.Morita, T.Kubo, H.Kitagawa, T.Okubo, T.Mitani, K.Nakasuji: "Complementary Double Hydrogen-Bonded CT Complexes of TTF Having Uracil Moiety"Synthetic Metals. (in press).

[Publications] M.Fujishima, R.Ikeda, S.Kanda, H.Kitagawa: "Electronic State of A Hydrogen-Doped Copper Coordination Polymer : catena-μ-N, N'-bis-(hydroxyethyl)dithiooxamidatocopper(II),(HOC_2H_4)_2dtoaCu"Mol.Cryst.Liq.Cryst.. 379. 223-228 (2002)

[Publications] Y.Nagao, R.Ikeda, S.Kanda, H.Kitagawa: "Complex-Plane Impedance Study on A Hydrogen-Doped Copper Coordination Polymer : N, N'-bis-(2-hydroxy-ethyl)dithiooxamidatocopper(II)"Mol.Cryst.Liq.Cryst.. 379. 89-94 (2002)

[Publications] A.Kobayashi, H.Kitagawa, R.Ikeda: "Structural and Optical Properties of Pt_2(dtp)_4Br_2 (dtp = dithiopropionato) and Its Halogen-Replacement Effect"Mol.Cryst.Liq.Cryst.. 379. 315-320 (2002)

[Publications] S.Takaishi, H.Kitagawa, R.Ikeda: "Relaxation Process of CT Exciton State in a One-Dimensional MX-Chain Compound 〔NiBr(chxn〕_2]Br^2"Mol.Cryst.Liq.Cryst.. 379. 279-284 (2002)

[Publications] R.Makiura, H.Kitagawa, R.Ikeda: "Electronic State of A Halogen-Bridged Mixed-Valence Binuclear Complex, Ni_2(dta)_4I"Mol.Cryst.Liq.Cryst.. 379. 309-314 (2002)

[Publications] M.Mitsumi, K.Kitamura, A.Morinaga, Y.Ozawa, M.Kobayashi, K.Toriumi, Y.Iso, H.Kitagawa, T.Mitani: "Novel Valence-Ordering Structures and Magnetic behavior of New Metallic MMX Chain Compounds"Angrew.Chem.Int.Ed.. 41. 2767-2771 (2002)

[Publications] Y.Morita, S.Maki, M.Ohmoto, H.Kitagawa, T.Okubo, T.Mitani, K.Nakasuji: "Hydrogen-Bonded Charge-Transfer Complexes of TTF Containing a Uracil Moiety : Crystal Structures and Electronic Properties of the Hydrogen Cyananilate and TCNQ Complexes"Organic Letters. 4. 2185-2188 (2002)

[Publications] G.Saito, H.Sasaki, T.Aoki, Y.Yoshida, A.Otsuka, H.Yamochi, O.Drozdova, K.Yakushi, H.Kitagawa: "Complex Formation of Ethylenedioxyethylenedithiotetrathiafulvalene (EDOEDT-TTF : EOET) and its self-assembling ability"J.Mater.Chem.. 12. 1640-1649 (2002)

[Publications] S.Takaishi, M.Kano, H.Kitagawa, Y.Furukawa, K.Kumagai, R.Ikeda: "Spin Structure and Dynamics in a Spin 1/2 One Dimensional Antiferromagnet, [NiBr(chxn)_2]Br_2"Chem.Lett. 856-857 (2002)

[Publications] H.Kitagawa, Y.Nagao, M.Fujishima, R.Ikeda, S.Kanda: "Highly Proton-Conductive Copper Coordination Polymer, H_2dtoaCu"Inorg.Chem.Commun.. 6. 346-348 (2003)

[Publications] M.Yamauchi, Y.Isobe, R.Ikeda, H.Kitagawa: "A Study on Hydrogen Adsorption of Polymer-Protected Pt Nanoparticles"Synth.Met.. (in press).

北川宏筑波大学, 化学系, 助教授 (90234244)