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

酞菁（Pc）配合物与轴向CN配体用于开发新的导体的基础上最初设计的逐步堆叠。当中心金属离子为非磁性Co^时，<III>可获得正常导体，而当中心金属离子为磁性Fe^时<III>，可获得磁性导体。[Co^<III>（Pc）（CN）_2]^-的电化学氧化产生中性自由基物种，其中Pc配体成为开壳结构。单独用该物种构建的晶体不是高导电的，而与溶剂分子共结晶由于有效的π-π堆积而提高了导电性。已经获得了取决于溶剂种类的各种堆叠结构。中性自由基晶体由于电子相关效应是半导体，而与阴离子（部分氧化盐）规范的金属导体结晶。它们的形成取决于阳离子种类，六种具有不同π-π堆积的部分氧化盐 关于我们 结构已经获得。[Co^<III>（Pc）（CN）_2]^-的电化学氧化得到了与Co盐同晶的晶体。对于一维体系，详细研究了钴盐和铁盐的物理性质。电子结构被发现是相同的热电功率和光学反射率测量的基础上。另一方面，电导率被发现是显着不同的彼此，电阻率几乎是恒定的钴盐，而它显示在低温下的铁盐的绝缘行为。这是由于在Pc环的中心存在周期性排列的磁矩。作为一个重要的结果，我们已经发现，电阻率下降，通过施加外部磁场。这样的一维系统表现出“巨负磁电阻”是不寻常的。少

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