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

以富硫二硫醇盐为配体的各种金属配合物作为扩展的π电子体系已经被合成，通过氧化反应，得到了新的电导体，并对其中一些化合物的磁性进行了研究。○环戊二烯基铑（Ⅲ）和环戊二烯基铱（Ⅲ）与C_3S_5或C_8H_4S_8配体的配合物，以及相应的五甲基环戊二烯基铑（Ⅲ）和环戊二烯基铱（Ⅲ）配合物。已经合成了金属络合物，并且通过与溴或碘反应获得了它们的氧化物。氧化过程中，导致二硫代配体为中心的氧化已被澄清。用X射线晶体结构分析和ESR谱研究了氧化产物的结构和性质，并测定了它们的电导率。合成了含Mn（II）离子的○ [Mn（C_8H_4S_8）_2]^<2->配合物。磁化率的计算结果表明，自旋态S = 5/2，在自旋态S = 5/2附近存在四面体结构。 ...更多信息 e Mn（II）离子处于固态。[Mn（C_8H_4S_8）_2]^0<2->与碘反应得到Mn（III）态的[Mn（C_8H_4S_8）_2]^0和单电子氧化的C_8H_4S_8配体，其自旋态为S = 3/2。该氧化物在配合物部分之间表现出强的反铁磁相互作用（Θ= -60 K），在室温下对压实的颗粒测量的电导率为3.0 × 10^<-2>S cm^<-1>。合成了极性金属配合物[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-去质子化的2-苯基吡啶; n = 1，2）。通过它们与碘或TCNQ反应获得的氧化物种显示出高电导率。[Au（ppy）（C_8H_4S_8）]经电解氧化得到的[Au（ppy）（C_8H_4S_8）]_2[PF_6]晶体在室温附近具有金属性。它们具有通过平面氧化C_8H_4S_8部分之间的S-S接触的二维相互作用形成的导电通路。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