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

以富硫二硫酸盐配体为扩展π-电子体系的各种金属配合物已被合成，通过氧化得到了新的电导体，并对其中一些材料的磁性能进行了澄清。〇与C_3S_5或C_8H_4S_8配体合成了环戊二烯铑（III）和-铱（III）配合物以及相应的五甲基环戊二烯金属配合物，并与溴或碘反应得到了它们的氧化态。阐明了导致二硫代盐中心氧化的氧化过程。通过x射线晶体结构分析和ESR光谱研究了氧化产物的结构和性能，并测量了它们的电导率。已合成了含有Mn（II）离子的[Mn(C_8H_4S_8)_2]^<2->配合物。磁化率明确了固体中S = 5/2的自旋态和围绕着…More e Mn（II）离子的四面体几何。[Mn(C_8H_4S_8)_2]^<2->配合物与碘反应，使[Mn(C_8H_4S_8)_2]^0具有Mn（III）态和单电子氧化的C_8H_4S_8配体，得到S = 3/2的自旋态。该氧化物质在复部分（Θ= -60 K）之间表现出强的反铁磁相互作用，在室温下测量的压实球团的电导率为3.0 × 10^<-2> S cm^<-1>。〇极性金属配合物[M(ppy)(L)]^<n-> (M = Pd(II), Pt（II）和Au(III)；L= C_3S_5^<2->或C_8H_4S_8^<2->；ppy = c_c -去质子化2-苯吡啶；N = 1,2)已合成。它们与碘或TCNQ反应得到的氧化态表现出高导电性。由[Au(ppy)(C_8H_4S_8)]电解氧化得到的[Au(ppy)(C_8H_4S_8)]_2[PF_6]晶体在室温附近表现出金属行为。它们通过平面氧化的C_8H_4S_8基团之间的S—S接触形成二维相互作用的导电途径。少

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