Design of Novel Superconductors and Magnetic Conductors Based on Stepwise π-Stacking Structures

基于阶梯式π堆叠结构的新型超导体和磁导体设计

• 批准号: 11304048
• 负责人: INABE Tamotsu
• 金额: $ 25.45万
• 依托单位: Hokkaido University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11304048/
• 关键词: Phthalocyanines; Electrical Conductor; Partially Oxidized Salts; π-π Stacking Structure; Local Magnetic Moment; Giant Magnetoresistance; Magnetic Conductor; 低次元導電体; 圧力依存性; 磁気抵抗; ナフタロシアニン; 一次元導電体; 強相関電子系; 中性ラジカル; 電子系の次元性; 導電体; 局在スピン; 電気伝導度

Phthalocyanine (Pc) complexes with axial CN ligands were utilized for development of novel conductors based on the originally devised stepwise stacking. When the central metal ion is nonmagnetic Co^<III> normal conductors can be obtained, while when it is magnetic Fe^<III> magnetic conductors can be obtained.Electrochemical oxidation of [Co^<III>(Pc)(CN)_2]^- yields the neutral radical species in which the Pc ligand becomes open-shell structure. The crystal constructed solely with this species was not highly conducting while co-crystallization with solvent molecules improved the conductivity due to the efficient π-π stacking. Various stacking structures depending on the solvent species have been obtained. The neutral radical crystals are semiconductors due to the electron correlation effect, while crystallization with the anion (partially oxidized salt) gage metallic conductors. Their formation depends on the cationic species, and six partially oxidized salts with various π-π stacking … More structures have been obtained. Among them the crystal with double two-dimensional sheeto structure has been found to maintain metallic character at low temperatures under high pressure.Electrochemical oxidation of [Co^<III>(Pc)(CN)_2]^- gave isomorphous crystals with the Co salts. For the one-dimensional system, the physical properties of the Co and Fe salts were investigated in detail. Electronic structure was found to be identical based on the thermoelectric power and optical reflectance measurements. On the other hand, the electrical conductivity was found to be dramatically different from each other , the resistivity is almost constant for the Co salt, while it shows insulating behavior at low temperature for the Fe salt. This is due to the existence of periodically arranged magnetic moments at the center of the Pc rings. As an important consequence, we have found that the resistivity decreases by applying external magnetic field. It is unusual that such a one-dimensional system shows "giant negative magnetoresistance". Less

具有轴向 CN 配体的酞菁 (Pc) 配合物被用于开发基于最初设计的逐步堆叠的新型导体。当中心金属离子为非磁性Co^<III>时，可以获得正常导体，而当中心金属离子为磁性时，可以获得磁性导体Fe^<III>。[Co^<III>(Pc)(CN)_2]^-的电化学氧化产生中性自由基物种，其中Pc配体变成开壳结构。单独用这种物质构建的晶体的导电性不高，而与溶剂分子共结晶由于有效的 π-π 堆叠而提高了导电性。已经获得了取决于溶剂种类的各种堆叠结构。由于电子相关效应，中性自由基晶体是半导体，而阴离子（部分氧化盐）结晶则成为金属导体。它们的形成取决于阳离子种类，并且已经获得了具有各种π-π堆积结构的六种部分氧化盐。其中双二维片状结构的晶体在低温高压下仍能保持金属特性。[Co^<III>(Pc)(CN)_2]^-的电化学氧化得到与Co盐的同形晶体。对于一维系统，详细研究了 Co 盐和 Fe 盐的物理性质。根据热电势和光反射率测量发现电子结构是相同的。另一方面，发现Co盐的电导率彼此显着不同，电阻率几乎恒定，而Fe盐在低温下表现出绝缘行为。这是由于 Pc 环中心存在周期性排列的磁矩。作为一个重要的结果，我们发现通过施加外部磁场电阻率会降低。这种一维系统表现出“巨大的负磁阻”是不寻常的。较少的

项目成果

芥川智行, 他: "Ionic Channel Structures in [(M^+)_x([18]crown-6)][Ni(dmit)_2]_2 Molecular Conductors"Chemistry A European Journal. 7. 4902-4912 (2001)

Tomoyuki Akutakawa 等人：“[(M^+)_x([18]crown-6)][Ni(dmit)_2]_2 分子导体中的离子通道结构”化学欧洲杂志 7. 4902-4912 ( 2001）

小林典仁, 他: "Synthesis, Electrical Properties of a Novel Ni-dithiolene Complex with Dimerized Structure"Synthetic Metals. 120. 1055-1056 (2001)

Norihito Kobayashi 等人：“具有二聚结构的新型 Ni-二硫醇络合物的合成、电性能”合成金属。 120. 1055-1056 (2001)

内藤俊雄, 他: "A New Molecular Metal Based on Pd(dmit)_2 : Synthesis, Structure and Electrical Properties of (C_7H_<13>NH)(Pd(dmit)_2]_2 (dmit^<2->=2-thioxo-1,3-dithiole-4,5-dithiolate)"Journal of Materials Chemistry. 11. 2199-2204 (2001)

Toshio Naito 等人：“基于 Pd(dmit)_2 的新型分子金属：(C_7H_<13>NH)(Pd(dmit)_2]_2 的合成、结构和电性能 (dmit^<2->= 2-硫代-1,3-二硫醇-4,5-二硫醇)”材料化学杂志.11.2199-2204(2001)

松島光一 他: "Crystal Structure of an Ionic Charge-Transfer Complex of DAP-F_4TCNQ (DAP=1,6-Diaminopyrene, F_4TCNQ=2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-p-quinodimethane)"Bulletin of the Chemistry Society of Japan. 73. 2231-2235 (2000)

Koichi Matsushima 等人：“DAP-F_4TCNQ 离子电荷转移复合物的晶体结构（DAP=1,6-二氨基芘，F_4TCNQ=2,3,5,6-四氟-7,7,8,8-四氰基） -p-醌二甲烷)”日本化学会会报.73.2231-2235(2000)

稲辺保: "Novel Phthalocyanine-based Conductors : Tunable π-π Stacking Structure Through the Steric and Chemical Interactions of Axial Ligands"Journal of Porphyrins and Phthalocyanines. 5. 3-12 (2001)

Tamotsu Inabe：“新型酞菁基导体：通过轴向配体的空间和化学相互作用可调节 π-π 堆叠结构”《卟啉和酞菁杂志》5. 3-12 (2001)。