Development of Electrical Conductors with Magnetisms Based on Metal Complexes with Sulfur-rich Dithiolate Ligands as an Extended π-Electron System

开发基于具有富硫二硫醇盐配体的金属配合物作为扩展π电子系统的磁性电导体

基本信息

批准号：
15550049
负责人：
MATSUBAYASHI Gen-etsu
金额：
$ 2.24万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2004
项目状态：
已结题

项目摘要

Various metal complexes with sulfur-rich dithiolate ligands as an extended π-electron system have been synthesized, and by the oxidation of them new electrical conductors have been obtained and for some of them the magnetic properties have been also clarified.○ Cyclopentadienyl-rhodium(III) and -iridium(III) complexes with the C_3S_5 or C_8H_4S_8 ligand as well as the related pentamethylcyclopentadienyl-metal complexes have been synthesized, and the oxidized species of them have been obtained by reactions with bromine or iodine. The oxidation process which leads to the dithiolate ligand-centered oxidation has been clarified. Structures and properties of the oxidized species have been studied by X-ray crystal structure analysis and ESR spectra, and their electrical conductivities have been measured.○ [Mn(C_8H_4S_8)_2]^<2-> complexes containing the Mn(II) ion have been synthesized. The magnetic susceptibilities have clarified the spin state of S = 5/2 and a tetrahedral geometry around th … More e Mn(II) ion in the solid state. The reaction of the [Mn(C_8H_4S_8)_2]^<2-> complex with iodine has afforded [Mn(C_8H_4S_8)_2]^0 having the Mn(III) state and the one-electron oxidized C_8H_4S_8 ligands, which results in the spin state of S = 3/2. This oxidized species exhibits strong anti-ferromagnetic interaction among the complex moieties (Θ= -60 K) with the electrical conductivity of 3.0 x 10^<-2> S cm^<-1> measured for a compacted pellet at room temperature.○ Polar metal complexes [M(ppy)(L)]^<n-> (M = Pd(II), Pt(II) and Au(III); L= C_3S_5^<2-> or C_8H_4S_8^<2->; ppy =_C-deprotonated 2-phenylpyridine; n = 1, 2) have been synthesized. The oxidized species obtained by reactions of them with iodine or TCNQ show high electrical conductivities. Crystals of [Au(ppy)(C_8H_4S_8)]_2[PF_6] obtained by the oxidation through electrolysis of [Au(ppy)(C_8H_4S_8)] exhibit metallic behavior near room temperature. They have an electrical conduction pathway formed by two-dimensional interaction through S--S contacts among the planar, oxidized C_8H_4S_8 moieties. Less

Various metal complexes with sulfur-rich dithiolate ligands as an extended π-electron system have been synthesized, and by the oxidation of them new electrical conductors have been obtained and for some of them the magnetic properties have been also clarified.○ Cyclopentadienyl-rhodium(III) and -iridium(III) complexes with the C_3S_5 or C_8H_4S_8 ligand as以及相关的五甲基甲基二烯基 - 金属复合物已合成，并且已经通过与溴或碘的反应获得了它们的氧化物物种。阐明了导致二硫酸盐配体氧化物的氧化过程。已经通过X射线晶体结构分析和ESR光谱研究了氧化物物种的结构和性能，并测量了它们的电导率。○[MN（C_8H_4S_8）_2]^<2-> <2->复合物已合成。磁敏感性阐明了s = 5/2的自旋态，在固态下的e Mn（ii）离子附近的四面体几何形状。 [Mn（C_8H_4S_8）_2]^<2->复合物与碘的反应得到了[Mn（C_8H_4S_8）_2]^0具有Mn（iii）状态和单位氧化物C_8H_4S_4S_8 LIGAND的反应。该氧化物种在复杂的部分（θ= -60 K）之间表现出强烈的抗铁磁相互作用，其电导率为3.0 x 10^<-2> s cm^<-1>在室温下对压实颗粒测量的测量。 C_3S_5^<2->或C_8H_4S_8^<2->;通过它们与碘或TCNQ的反应获得的氧化物种显示高电导率。 [AU（PPY）（C_8H_4S_8）] _ 2 [PF_6]的晶体通过氧化通过[AU（PPY）（C_8H_4S_8）的氧化而获得的晶体，在室温附近暴露的金属行为。它们具有通过平面之间的S-S接触二维相互作用形成的电传导途径，氧化了C_8H_4S_8部分。较少的