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

• 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
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550049/
• 关键词: Dithiolate complex; Rhodium complex; Iridium complex; Gold complex; Platinum complex; Manganese complex; Electrical conductivity; Magnetic susceptibility; クロム錯体; シクロペンタジエニル錯体; X線結晶解析

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

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反应获得的氧化物表现出高电导率。[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

项目成果

Oxidation of [Ir(η^5-C_5Me_5)(C_8H_4S_8)] and Crystal Stuctures of [IrI-(η^5-C_5Me_5)(C_8H_4S_8)](I_3) and [IrI-(η^5-C_5Me_5)(C_8H_4S_8)](I_3)_<1/2>(I_7)_<1/2>

[Ir(η^5-C_5Me_5)(C_8H_4S_8)]的氧化和[IrI-(η^5-C_5Me_5)(C_8H_4S_8)](I_3)和[IrI-(η^5-C_5Me_5)(C_8H_4S_8)的晶体雕像](I_3)_<1/2>(I_7)_<1/2>

• 发表时间: 2005
• 期刊: Inorg.Chim.Acta 358
• 作者: K.Kawabata;M.Nakano;H.Tamura;G.Matsubayashi
• 通讯作者: G.Matsubayashi

ESR study of spin-crossover complex [MnIII(taa)] using pulsed high magnetic field

使用脉冲强磁场研究自旋交叉络合物 [MnIII(taa)] 的 ESR

• DOI: 10.1016/j.jmmm.2003.12.1334
• 发表时间: 2004
• 期刊: Journal of Magnetism and Magnetic Materials
• 影响因子: 2.7
• 作者: S. Kimura;T. Otani;Y. Narumi;K. Kindo;M. Nakano;G. Matsubayashi
• 通讯作者: G. Matsubayashi

Oxidation of [Ir(η^5-C_5Me_5)-(C_5Me_5)] and Crystal Structures of [IrI(η^5-C_5Me_5)-(C_8H_4S_8)](I_3) and [IrI(η^5-C_5Me_5)(C_8H_4S_8)](I_3)_<1/2>(I_7)_<1/2>

[Ir(η^5-C_5Me_5)-(C_5Me_5)] 的氧化以及 [IrI(η^5-C_5Me_5)-(C_8H_4S_8)](I_3) 和 [IrI(η^5-C_5Me_5)(C_8H_4S_8) 的晶体结构](I_3)_<1/2>(I_7)_<1/2>

• 发表时间: 2005
• 期刊: Inorg.Chim.Acta 358
• 作者: K.Kawabata;M.Nakano;H.Tamura;G.Matsubayashi
• 通讯作者: G.Matsubayashi

X-ray Crystal Structure and Electrical Conductivity of [Au(ppy)(C_8H_4S_8)]_2-[PF_6] [ppy^- = C-Deprotonated-2-phenyl-pyridine(-); C_8H_4S_8^<2-> = 2-{(4,5-Ethylenedi-thio)-1,3-dithiole-pyridine(-); 2-ylideile}-1,3-dithiole-4,5-dithionate(2-)]

[Au(ppy)(C_8H_4S_8)]_2-[PF_6] [ppy^- = C-去质子化-2-苯基-吡啶(-)的X射线晶体结构和电导率；

• 发表时间: 2003
• 期刊: Eur.J.Inorg.Chem. 22-No.2
• 作者: K.Kubo;M.Nakano;H.Tamura;G.Matsubayashi
• 通讯作者: G.Matsubayashi

Properties of Organometal-Sulfur-rich Dithiolate Complexes [M(L)(C_8H_4S_8)] (M = Rh^<III> and Ir^<III>;L = η^5-C_5H_5 and η^5-C_5Me_5) and Their Oxidation

富含有机金属硫的二硫醇配合物[M(L)(C_8H_4S_8)] (M = Rh^<III> 和 Ir^<III>;L = η^5-C_5H_5 和 η^5-C_5Me_5) 的性质及其氧化

• 发表时间: 2004
• 期刊: Eur.J.Inorg.Chem.
• 作者: K.Kawabata;M.Nakano;H.Tamura;G.Matsubayashi
• 通讯作者: G.Matsubayashi