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

作为一种扩展的π-电子体系，合成了多种富硫二硫配体的金属配合物，通过氧化得到了新的导电体，并阐明了它们的磁性。合成了C_3S_5或C_8H_4S_8配体的环戊二烯-Rh(III)和-Ir(III)配合物以及相关的五甲基环戊二烯-金属配合物，它们的氧化物种是通过与溴或碘反应得到的。阐明了导致以二硫代硫酸酯为中心的氧化反应过程。用X-射线晶体结构分析和ESR谱研究了被氧化物种的结构和性质，并测定了它们的电导率。合成了0个[Mn(C_8H_4S_8)_2]&lt；2-&gt；含Mn(II)的配合物。磁化率阐明了S=5/2的自旋态和Th…周围的四面体构型固相中有较多的e-Mn(II)离子。[Mn(C_8H_4S_8)_2]&lt；2-&gt；与碘反应生成了具有Mn(III)态的[Mn(C_8H_4S_8)_2]^0和单电子氧化的C_8H_4S_8配体，导致S=3/2的自旋态。这些氧化物种在络合物部分(Θ=-60K)之间表现出很强的反铁磁相互作用，其电导率为3.0x10^&lt；-2&gt；S cm^&lt；-1&gt；合成了极性金属配合物[M(Ppy)(L)]^&lt；n-&gt；(M=Pd(II)，Pt(II)和Au(III)；L=C_3S_5^&lt；2-gt；或C_8H_4S_8^&lt；2-&gt；ppy=_C-去质子化2-苯基吡啶；n=1，2)。它们与碘或TCNQ反应得到的氧化物种具有较高的电导率。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。它们具有一条通过S-S接触在平面上氧化的C_8H_4S_8部分之间通过二维相互作用形成的导电路径。较少

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