Development of Electrical Conductors with Multi-dimensionality Based on Non-planar Metal Complexes with Sulfur-rich Ligands as an Extended pi-System

基于富硫配体非平面金属配合物作为扩展 pi 系统的多维导电体的开发

• 批准号: 09640665
• 负责人: MATSUBAYASHI Gen-etsu
• 金额: $ 1.98万
• 依托单位: Oasaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09640665/
• 关键词: Dithiolate complex; Molybdenum complex; Platinum complex; Cobalt complex; Titanium complex; Ruthenium complex; Oxidation; Electrical conductivity; シクロペンタジエニル錯体; スズ錯体; 酸化還元電位

Various metal complexes with dithiolato ligands containing many sulfur atoms asan extended it-system have been synthesized, and by the oxidation of them new electrical conductors have been obtained and their properties c1arified.[NEt_4]_2[Mo(O)(etdt)_2](etdt=C_8H_4S_4^<2->) having five-coordinate square-pyramid geometry has been prepared. The oxidized species [NEt_4]_<0.3>[Mo(O)(etdt)_2] and [Fe(C_5Me_5)_2]_<0.05>[Mo(O)(etdt)_2] exhibited high electrical conduc-tivities (0.29 and 5.9 S cm^<-1>, respectively, at room temperature for compacted pellets). In the oxidized species S-S interactions among the etdt-ligand moieties form effective electron-conduction pathways.Co(III)- and Ti(IV)- complexes having cyclopentadienyl groups and dmit (C_3S_5^<2->) or etdt ligand have been investigated.Oxidation behavior of reactions of Co (L) (dmit) (L = eta^5-C_5H_5, eta^5-C_5Me_5) with bromine and the crystal structure of the one-electron oxidized species Co(eta^5-C_5Me_5)(dmit)Br have been clarifie … More d, together with a strong antiferromagnetic interaction between the oxidized dmit-ligand moieties.Co(eta^5-C_5H_5)(etdt) and Ti(eta^5-C_5H_5)_2(etdt) have been synthesized and properties of their oxidized complexes studied. Especially, [Co(eta^5-C_5H_5)(etdt)] I_3 and [Co(eta^5-C_5H_5)(etdt)][PF_6]_<0.7> exhibited high electrical conductivities of 0.19 and 0.16 S cm^<-1>,respectively, at room temperature measured for compacted pellets.Electrical conductivities of oxidized species of dmit- and etdt-Ru(II) cpmplexes have been studied. Ru(bpy)_2(dmit) and Ru(bpy)_2(etdt) (bpy = 2,2'-bipyridine) having a bulky six-coordinate geometry have been synthesized. The oxidized species obtained by reactions with iodine, Ru(bpy)_2(etdt)] I and Ru(bpy)_2(etdt)] (I_3)_<2.1>, have electrical conductivities of 7.4 x 10^<-7> and 7.0 x 10^<-4> S cm^<-1>, respectively. Even in the highly bulky complexes coordinated with two bpy ligands, extended oxidation on the etdt-ligand moiety leads to effective molecular interaction through S-S contacts among etdt-Iigand moieties. Less

已经合成了各种包含许多硫原子Asan扩展IT系统的二硫醇配体的金属配合物，并通过它们的氧化获得了新的电导体及其特性C1ar。已准备就绪。氧化的物种[net_4] _ <0.3> [mo（o）（etdt）_2]和[fe（c_5me_5）_2] _ <0.05> [mo（o）（eTDT）_2]暴露了高电导性接触性（0.29和5.9 s cm^<-1> <-1>>室温度）。在氧化的物种中，ETDT-配合部分之间的S-S相互作用形成了有效的电子传导途径。 ETA^5-C_5ME_5）含溴和单电子氧化物物种CO（ETA^5-C_5ME_5）（DMIT）BR的晶体结构已被澄清……更多的D，以及强烈的抗fiferromagnetic相互作用，氧化dmit-ligandies.co（eta^5-C_5H_5）（ETA^5-C_5H_5）（ET） Ti（ETA^5-C_5H_5）_2（ETDT）已合成并具有氧化物配合物的特性。特别是，[CO（ETA^5-C_5H_5）（ETDT）] I_3和[CO（ETA^5-C_5H_5）（ETDT）] [PF_6] _ <0.7>在室温下，分别在室温下，分别暴露于0.19和0.16 s cm^<-1>的高电导率的高电导率，用于室内温度，用于室温下的dimit.smit.smitctim and contictim of dimit and dimit and dimit and dimmit contim.ectim and。 ETDT-RU（II）CMPPLEX已经研究了。 RU（BPY）_2（DMIT）和RU（BPY）_2（ETDT）（bpy = 2,2'-二吡啶）具有笨重的六坐标几何形状。通过与碘的反应获得的氧化物种，Ru（bpy）_2（etdt）] I and Ru（bpy）_2（etdt）]（i_3）_ <2.1>，具有7.4 x 10^<-7> 7>和7.0 x 10^10^<-4> s cm^<-4> s cm^<-1>的电导率为7.4 x 10^<-7> 7>。即使在与两个BPY配体配位的高度笨重的复合物中，ETDT系部分中的氧化也会通过ETDT-IIGAND部分之间的S-S接触来有效地分子相互作用。较少的

项目成果

中野元裕: "Preparation and properities of C_8H_4S_8-platinum (II) complexes and electrical conductivities of their oxidized species and X-ray crystal structure of C_8H_4S_8 (CH_2CH_2CN) _2 as a pro-ligand compound" Inorganica Chimica Acta. (印刷中).

Motohiro Nakano：“C_8H_4S_8-铂 (II) 配合物的制备和性质及其氧化物质的电导率以及作为配体化合物的 C_8H_4S_8 (CH_2CH_2CN) _2 的 X 射线晶体结构”Inorganica Chimica Acta（正在出版）。

H.Mori, M.Nakano, H.Tamura, and G.Matsubayashi: "Oxidation Properties of Co (eta^5-C_5H_5) - (C_8H_4S_8) and CoL (C_3S_5) (L=eta^5-C_5H_5and eta^5-C_5Me_5) and Crystal Structure of Co(eta^5-C_5H_5) (C_3S_5) Br." J.Organomet.Chem.574-No.1. 77-85 (1999)

H.Mori、M.Nakano、H.Tamura 和 G.Matsubayashi：“Co (eta^5-C_5H_5) - (C_8H_4S_8) 和 CoL (C_3S_5) 的氧化性质（L=eta^5-C_5H_5 和 eta^5-

M.Nakano, A.Kuroda, H.Tamura, R.Arakawa, and G.Matsubayashi: "Preparation and Properties of C_8H_4S_8-platinum (II) Complexes and Electrical Con-ductivities of Their Oxidized Species and X-ray Crystal Structure of C_8H_4S_8(CH_2CH_2CN)_2 as a Pro-ligand C

M.Nakano、A.Kuroda、H.Tamura、R.Arakawa 和 G.Matsubayashi：“C_8H_4S_8-铂 (II) 配合物的制备和性质及其氧化物的电导率和 C_8H_4S_8 的 X 射线晶体结构

A.Nakahama, M.Nakano, and G.Matsubayashi: "Properties of Pt (III) -complexes Containing Both a Pyridyl N-N Chelate Ligand Having a Long Alkyl Chain and a Sulfur-rich Dithiolate Ligand and their Molecular Interactions in the Solid State." Inorg.Chim.Acta.

A.Nakahama、M.Nakano 和 G.Matsubayashi：“含有长烷基链的吡啶基 N-N 螯合配体和富硫二硫醇配体的 Pt (III) 配合物的性质及其在固态下的分子相互作用。

森 博之: "Oxidation Properties of Co(η^5-C_5H_5)(C_8H_4S_8)and CoL(C_3S_5)(L=η^5-C_5H_5 and η^5-C_5Me_5)and C_8H_4S_8^<2->)and crystal structur of Co(η^5-C_5H_5)(C_3S_5)Br," Journal of Organometallic Chemistry. 574・1. 77-85 (1999)

Hiroyuki Mori：“Co(η^5-C_5H_5)(C_8H_4S_8)和CoL(C_3S_5)(L=η^5-C_5H_5和η^5-C_5Me_5)和C_8H_4S_8^<2->)的氧化性质和晶体结构Co(η^5-C_5H_5)(C_3S_5)Br，《有机金属化学杂志》. 574・1. 77-85 (1999)