Construction of Three-Dimensional Organic Molecular Metals and Realization of Superconductivity

三维有机分子金属的构建与超导的实现

• 批准号: 11640581
• 负责人: MISAKI Yohji
• 金额: $ 2.3万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11640581/
• 关键词: Tetrathiapentalene; Donor; Organic Conductor; Electrical Conductivity; X-Ray Structure Analysis; Band Calculation; Superconductivity

The main purpose of this research is construction of molecular metals with three-dimensional electronic structure by means of chemical modification to tetrathiapentalene (TTP) type donors which are known to have a strong tendency to give two-dimensional metals. The obtained results are as follows.(1) It has been found that TM-TPDS and TM-PDS afford cation radical salts with three-dimensional molecular array by means of orthogonally arranged one-dimensional stacks. Most of them show metallic electrical conductivity, and exhibit metal to semiconductor transition in the low temperature region.(2) SM-(T) PDT and SM-(T) PDS with the selenomethyl group have been synthesized, and their cation radical salts have been prepared. X-Ray structure analyses of (SM-PDT) X (PhCl)m(X=PF_6, AsF_6) reveal that they are quasi two-dimensional conductors, in which selenium-selenium contacts in the selenomethyl groups along the donor long axis are observed. Though this salt was also semiconductors owing to 1 : 1 composition, these salts exhibit considerably high conductivity of 10^0 S cm^<-1> at room temperature.(3) TTP dimer is an interesting molecular system which is expected to be realized three-dimensional intermolecular interaction by the so-called spanning overlap thanks to the long molecular length as well as the side-by-side interaction. Then, TTP dimer with alkyldithio unit as a spacer have been synthesized, and their electrochemical property was clarified by cyclic voltammetry.The papers which summarized the results mentioned above have been submitted except for the part.

本研究的主要目的是通过化学修饰四硫并环戊二烯（TTP）型给体来构建具有三维电子结构的分子金属，已知TTP型给体具有强烈的二维金属倾向。所得结果如下。(1)研究发现，TM-TPDS和TM-PDS通过一维正交排列的堆积，形成了具有三维分子阵列的阳离子自由基盐。它们中的大多数显示出金属导电性，并在低温区显示出金属到半导体的转变。(2)合成了含硒甲基的SM-（T）PDT和SM-（T）PDS，并制备了它们的阳离子自由基盐。X射线结构分析表明，（SM-PDT）X（PhCl）m（X=PF_6，AsF_6）为准二维导体，其中硒甲基基团沿着施主长轴存在硒-硒接触。虽然这种盐也是半导体，由于1：1的组成，这些盐在室温下表现出相当高的电导率10^0 S cm^3<-1>。(3)TTP二聚体是一种有趣的分子体系，由于其分子长度较长，同时又具有相互作用，因此有望通过所谓的跨越重叠实现分子间的三维相互作用。在此基础上，合成了以烷基二硫代单元为间隔基的TTP二聚体，并通过循环伏安法对其电化学性质进行了研究。

项目成果

Y.Misaki: "A Novel Organic Conductor with Three-Dimensional Molecular Array : (TM-TPDS)_2AsF6"Chemistry Letters. 1274-1275 (2000)

Y.Misaki：“具有三维分子阵列的新型有机导体：(TM-TPDS)_2AsF6”化学快报。

K.Takahashi: "New TTP Donors Containing Chaleogenopyran-4-ylidene : Preparation, Structure, and Electrical Properties"Molecular Crystals and Liquid Crystals. (印刷中).

K. Takahashi：“含有 Chaleogenopyran-4-ylidene 的新型 TTP 供体：制备、结构和电性能”分子晶体和液晶（正在出版）。

Y.Misaki: "Tetrathiapentalene Type Donors as Promising π-Electron Framework for Organic Metals Stable down to Low Temperatures"Molecular Crystals and Liquid Crystals. (印刷中).

Y.Misaki：“四硫五烯型供体作为有机金属在低温下稳定的有前途的 π 电子框架”分子晶体和液晶（正在出版）。

K.Takahashi: "A Novel Organic Conductor with Two-Dimensional Molecular Array by the "Edge-to-Edge" Donor Interaction."Chem.Lett.. 126-127 (2001)

K.Takahashi：“通过“边对边”供体相互作用形成二维分子阵列的新型有机导体。”Chem.Lett.. 126-127 (2001)

Y.Misaki: "Tetrathiapentalene Type Donors a Promising π-Electron Framework for Organic Metals Stable down to Low Temperatures"Malecular Crystals and Liquid Crystals. (印刷中).

Y. Misaki：“四硫五烯型供体为在低温下稳定的有机金属提供了有前景的 π 电子框架”男性晶体和液晶（正在出版）。