複合機能有機材料(超伝導・スピン液体・新規相転移等)の開発

2003 Fiscal Year Annual Research Report

• Project/Area Number: 15205019
• Research Category: Grant-in-Aid for Scientific Research (A)
• Research Institution: Kyoto University
• Principal Investigator: 齋藤 軍治 京都大学, 大学院・理学研究科, 教授 (40132724)
• Co-Investigator(Kenkyū-buntansha): 大塚 晃弘 京都大学, 低音物質科学研究センター, 助手 (90233171) ; 前里 光彦 京都大学, 大学院・理学研究科, 助手 (60324604) ; 矢持 秀起 京都大学, 大学院・理学研究科, 助教授 (20182660)
• Keywords: 分子性超伝導体 / 一軸性歪み / スピン液体 / 金属-絶縁体転移 / 光誘起相転移 / イオン性液体 / 双性化合物 / フラーレン

Research Abstract

擬二次元三角格子構造を持ち、超伝導相に隣接するスピン液体_κ-(ET)_2Cu_2(CN)_3の^<13>C NMR測定を行なった。^1H NMR測定と同様に磁気秩序は観測されなかったが、5K以下でNMR吸収線の発散が確認された。内部磁場の静的な不均一性に由来すると考えられる。低対称分子EOET-TTFを用いて、三角格子構造を持つ_κ-(EOET-TTF)_2GaCl_4を得た。約40Kで金属-絶縁体転移が起きるが、2Kまで磁気秩序は観測されなかった。幾何学的フラストレーションとの関係については現在検討中である。
分子変形を伴った金属-絶縁体転移を示す(EDO-TTF)_2PF_6の低温(絶縁)相にレーザー光を照射したところ、極めて高効率かつ超高速に光誘起相転移が起きることを見出した。湿度により伝導性が変化する(BO)_2Br(H_2O)_3単結晶を用いて、導電性と格子定数の湿度異存性を検討した。その結果、湿度依存挙動が結晶表面のみに起因する現象ではなく、結晶内部にまで及ぶ結晶水の出入りによるものであることが判った。
EMI陽イオンを用いて作成した室温溶融塩(EMI)X(X=N(CN)_2,C(CN)_3,GaCl_4)が低粘性(13-18cP)ならびに高イオン導電性(1.8-2.7×10^<-2>Scm^<-1>)を示すことを明らかにした。
インドリンとトリシアノキノジメタン(3CNQ)誘導体がπ結合で結ばれたD-π-A分子内電荷移動錯体を作成した。3CNQの置換基によって電荷移動度(δ)が変化し、そのδから予想される分子(超)分極率が、分子軌道計算から見積もった数値とよく一致することを見出した。
新規イオン性C_<60>錯体(Cp^*_2Co^+)_2(C_<60>^<2->)(PhCN/PhCl_2)_2を得た。結晶構造解析から、8つのCp^*_2Co分子がC_<60>に配位しており、その結果三方向に交互積層鎖を形成していることを見出した。

Research Products

• [Publications] G.Saito: "Ionicity of Intramolecular Charge-Transfer Molecule D^<δ+>-π-A^<δ-> Based on 1,3,3-Trimethyl-2-methyleneindoline and 7,7,8,8-Tetracyanoquinodimethane"Journal of the American Chemical Society. 125・5. 1134-1135 (2003)
• [Publications] Y.Yoshida: "Optical and Magnetic Properies of Ionic Charge Transfer Complexes Based on 1,2-Dicyano[60]fullerene"Journal of Materials Chemistry. 13・2. 252-257 (2003)
• [Publications] S.Setifi: "First Radical Cation Salt of Paramagnetic Transition Metal Complex Containing TTF as Ligand, [Cu^<II>(hfac)_2(TTF-py)_2](PF_6)・2CH_2Cl_2(hfac=Hexafluoroacetylacetnate and TTF-py=4-(2-Tetrathiafulvalenyl-ethenyl)pyridine)"Inorganic Chemistry. 42・6. 1791-1793 (2003)
• [Publications] T.Akutagawa: "Hydrogen-bonded Supramolecular (2,2'-Bi-1H-benzimidazole)(2-(2-1H-Benzimidazolyl)-1H-benzimidazolium^+)_2(Cl^-) as an Electron Donor in a TCNQ Complex"CrystEngComm. 5. 54-57 (2003)
• [Publications] Y.Ogata: "Structural Features of a Clay Film Hybridized with a Zwitterionic Molecule as Analyzed by Second-Harmonic Generation Behavior"Clays and Clay Minerals. 51・2. 181-185 (2003)
• [Publications] D.V.Konarev: "Crystal Structure and Magnetic Properties of an Ionic C_<60> Complex with Decamethylcoba-1 tocene : (Cp_2^*Co)_2C_<60>(C_6H_4Cl_2, C_6H_5CN)_2・Singlet-Triplet Transitions in the C_<60>^<2-> Anion"Inorganic Chemistry. 42・12. 3706-3708 (2003)
• [Publications] Y.Yoshida: "Crystal Structures and Physical Properties of Cation Radical Salts of Ethylenedioxy-ethylene-dithio-tetrathiafulvalene (EDOEDT-TTF or EOET) : α'-(EOET)_2AuBr_2 and β"-(EOET)_2AuBr_2"Molecular Crystals and Liquid Crystals. 393. 105-118 (2003)
• [Publications] A.Ishikawa: "Electron Correlation and Two Dimensionality in the Spin-Density-Wave Phase of (TMTTF)_2Br Under Pressure"Physical Review B. 67・21. 212404/1-212404/4 (2003)
• [Publications] D.V.Konarev: "Formation of Single-Bonded (C_<60>^-)_2 and (C_<70>^-)_2 Dimers in Crystalline Ionic Complexes of Fullerenes"Journal of the American Chemical Society. 125・33. 10074-10083 (2003)
• [Publications] E.Shinohara: "A Novel Electron Conductive Nanocomposite, BEDO-TTF-Tetrasilicicfluormica"Solid State Communications. 127・6. 407-410 (2003)
• [Publications] D.V.Konarev: "The Interaction of C_<60>, C_<70>, and C_<60>(CN)_2 Radical Anions with Cobalt(II) Tetraphenylporphyrin in Solid Multicomponent Complexes"Chemistry -A Europien Journal. 9・16. 3837-3848 (2003)
• [Publications] Y.Shimizu: "Spin Liquid State in an Organic Mott Insulator with a Triangular Lattice"Physical Review Letters. 91・10. 107001/1-107001/4 (2003)
• [Publications] D.V.Konarev: "Ionic Multi-Component Complexes Containing TDAE^<・+> and C_<60>^<・-> Radical Ions and Neutral D_1 Molecules : D_1・TDAE・C_<60>"Dalton Transactions. 20. 3886-3891 (2003)
• [Publications] L.Ouahab: "One Dimensional Face-to-Face Stacking of Anderson-Evans[Cr(OH)_6Mo_6O_<18>]^<3-> Polyoxometalate Anion : Synthesis, Structure, and Physical Properies of (BEDT-TTF)_4[Cr(OH)_6Mo_6O_<18>]・2H_2O"Journal of Cluster Science. 14・3. 193-204 (2003)
• [Publications] A.Ishikawa: "Magnetic field dependence of incommensurate SDW transition in (TMTTF)_2Br"Synthetic Metals. 133-134. 65-66 (2003)
• [Publications] O.Drozdova: "Infrared Study of the Properties of the Normal (Metallic) Phase of κ-(ET-^<13>C_4)_2Cu(CN)[N(CN)_2]"Synthetic Metals. 133-134. 119-121 (2003)
• [Publications] Y.Shimojo: "Upper Critical Fields of Pressurized Organic Superconductors κ-(BEDT-TTF)_2X in the Magnetic Field Parallel to the Layer"Synthetic Metals. 133-134. 197-200 (2003)
• [Publications] Y.Shimizu: "Transport Properties of a Mott Insulator κ-(ET)_2Cu_2(CN)_3 under the Uniaxial Strain"Synthetic Metals. 133-134. 225-226 (2003)
• [Publications] T.Ishikawa: "Uniaxial Strain Study of κ-(BEDT-TTF)_2Cu(NCS)_2"Synthetic Metals. 133-134. 227-228 (2003)
• [Publications] O.Drozdova: "Spectroscopic Study of the [0110] Charge Ordering in (EDO-TTF)_2PF_6"Synthetic Metals. 133-134. 277-279 (2003)
• [Publications] K.Balodis: "Single Component Betainic Conductor : Pyrimido-Fused TTF Derivatives Having Ethylenedioxy Group"Synthetic Metals. 133-134. 353-355 (2003)
• [Publications] K.Nishimura: "Variable Band Filling in Organic Conductor with Proton Donor/Acceptor H_nTNBP^<(2-n)-> (TNBP:3,3',5,5'-Tetranitro-4,4'-biphenyldiol)"Synthetic Metals. 133-134. 437-439 (2003)
• [Publications] S.Sekizaki: "Variety of BEDT-TTF Salts with Organic Polycyano Anions"Synthetic Metals. 133-134. 455-457 (2003)
• [Publications] A.Ota: "A Novel Metal-Insulator Transition in (EDO)_2X (X=PF_6, AsF_6)"Synthetic Metals. 133-134. 463-465 (2003)
• [Publications] Y.Ogata: "A Novel Film with a Non-Centrosymmetric Molecular Alignment of D-π-A Zwitter Ionic Molecules Fabricated at an Air-Water Interface"Synthetic Metals. 133-134. 671-672 (2003)
• [Publications] Y.Yoshida: "Magnetic Properties of [70]Fulleride Compounds"Synthetic Metals. 133-134. 703-705 (2003)
• [Publications] D.V.Konarev: "First Ionic Multi-Component Complex of Fullerene C_<60>(C)_2 With Co(II)tetraphenylporphyrin and Bis(benzen)chromium"Synthetic Metals. 133-134. 707-709 (2003)
• [Publications] H.Ito: "Shubnikov-de Haas Oscillations in the Superconducting Fluctuation Region of κ-(BEDT-TTF)_2Cu(NCS)_2"Physica C. 388-389. 593-594 (2003)
• [Publications] Y.Shimojo: "Non-Saturating Upper Critical Field of Organic Superconductor κ-(BEDT-TTF)_2Cu[N(CN)_2]Cl"Physica C. 388-389. 605-606 (2003)
• [Publications] Y.Morita: "The First TTF Derivatives with Imidazole Moieties for Hydrogen-Bonded Charge-Transfer Complexes"Synthetic Metals. 135-136. 579-580 (2003)
• [Publications] Y.Morita: "Synthesis and Crystal Structure of CT Salt of Halogenated 1,6-Dithiapyrene"Synthetic Metals. 135-136. 581-582 (2003)
• [Publications] C.-H.Chong: "Property of Intramolecular Charge Transfer Compounds D^<δ+>-π-A^<δ-> Derived from TCNQ Derivatives"Synthetic Metals. 135-136. 603-604 (2003)
• [Publications] H.Yamochi: "A New Packing Pattern of the Conducting BEDO-TTF Complexes"Synthetic Metals. 135-136. 605-606 (2003)
• [Publications] S.Sekizaki: "TMTSF Salts with Polycyano Organic Anions without Bechgaard Structures"Synthetic Metals. 135-136. 631-632 (2003)
• [Publications] A.Ota: "Low Temperature Phase of a New Type Metal-Insulator Transition System"Synthetic Metals. 135-136. 643-644 (2003)
• [Publications] Y.Morita: "1,3-Diazaphenalenes : A New Donor System for Hydrogen-Bonded Charge-Transfer Complexes"Synthetic Metals. 135-136. 657-658 (2003)
• [Publications] D.V.Konarev: "The Formation of Single-Bonded (C_<60>^-)_2 and (C_<70>^-)_2 Dimers in Ionic Comlexes of Fullerenes"Synthetic Metals. 135-136. 781-782 (2003)
• [Publications] H.Ito: "Resistivity Anisotropy and Phase Diagram of the κ-type BEDT-TTF Salts"Synthetic Metals. 135-136. 1221-1222 (2003)
• [Publications] Y.Yoshida: "Crystal Structure and Physical Properties of α'-(EOET)_2AuBr_2"Synthetic Metals. 135-136. 1241-1242 (2003)
• [Publications] M.Maesato: "Anisotropy in the Superconducting Transition Temperature of κ-(BEDT-TTF)_2X"Synthetic Metals. 135-136. 1243-1244 (2003)
• [Publications] Y.Shimizu: "Magnetic properties of κ-(ET)_2Cu_2(CN)_3"Synthetic Metals. 135-136. 1247-1248 (2003)
• [Publications] Y.Yoshida: "1-Ethyl-3-methylimidazolium Based Ionic Liquids Containing Cyano Groups : Synthesis, Characterization, and Crystal Structure"Inorganic Chemistry. 43・4. 1458-1462 (2004)
• [Publications] 齋藤軍治: "シリーズ有機化学の探検「有機導電体の化学-半導体、金属、超伝導体」"丸善株式会社. 230 (2003)
• [Publications] 斎藤軍治: "イオン性液体-開発の最前線と未来-"シーエムシー出版. 7 (2003)
• [Publications] 斎藤軍治: "ナノ・IT時代の分子機能材料と素子開発"株式会社エヌ・ティー・エス. 20 (2004)