Development of organic superconductors and multifunctional supramolecules based on new π-elecfron systems

基于新型π电子体系的有机超导体和多功能超分子的发展

• 批准号: 15550127
• 负责人: NISHIKAWA Hiroyuki
• 金额: $ 2.24万
• 依托单位: University of Tsukuba (2004)Tokyo Metropolitan University (2003)
• 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-15550127/
• 关键词: Organic Conductor; Superconductor; Charge Order; Phase Diagram; Supramolecule; Intramolecular charge transfer; Organic Thin Film; Organic Solar Cell; π電子系; 電子供与体; ドナー-アクセプター系

In this research project, development of new organic conductors and superconductors based on new molecular design that is destabilization of stable molecular metals as seen in TTP(tetrathiafulvalen) and TTP(tetrathiapentalene) conductors has been conducted. For this purpose, new π-electron donors whose π-electron systems are reduce compared with those of the previous TTF and TTP donors have been designed and synthesized. Structures and physical properties of the conducting radical salts prepared from such π-reduced electron donors have been investigated and a new superconductor, (DODHT)_2BF_4・H_2O, was discovered. By investigating the insulating phase at ambient pressure of the pressure-induced superconductor, (DODHT)_2PF_6, by X-ray diffraction and magnetic susceptibility measurements, the insulator phase was a charge ordering state with stripe type charge pattern. Furthermore, measurement of the transport properties of this material under pressure more precisely, particularly around … More the boundary between superconducting and insulator phases, leads to the pressure-temperature phase diagram ; In the phase diagram, the superconducting and normal resistive states coexists above the pressure of 13 kbar, and the insulator phase exists immediately above the superconducting phase between 13.2 and 15.1 kbar. Because the clear insulator transition was observed in the transport measurement up to 8 kbar, the charge ordering insulator might spread over high pressure region at least 8 kbar. These results suggested that the charge fluctuation might be crucial to the superconductivity in this material and the present material will seive as a simple tool for the investigation of the universality of the interplay between superconductivity and charge fluctuation.With studying the molecular conductors, development of multifunctional supuramolecular materials and their application to the organic devices have been carried out. For such materials, donor-acceptor linked molecules, such as C_<60>-TTF dyads, were newly prepared and an obvious intramolecular charge transfer interaction was observed unlike the previously reported C_<60>-TTF systems. The life time of the photo-induced charge separated state of the C_<60>-TTF dyad was revealed to be extremely short by the photo-physical study of the excited states, which is disadvantageous for the organic devices such as an organic solar cell. In order to overcome this situation, C_<60>-TTF dendrimers were prepared and the solar cell property was observed in spite of the low efficiency. Less

在该研究项目中，基于新分子设计的新有机导体和超导体的开发是对TTP（Tetrathiafulvalen）和TTP（Tetrathiapentalene）导体的稳定分子金属不稳定的。为此，与先前的TTF和TTP供体的π电子系统相比，其π电子系统的新π电子供体已被设计和合成。已经研究了由此类π还原电子供体制备的激进销售的结构和物理性质，并发现了新的超导体（DODHT）_2BF_4・H_2O。通过在压力诱导的超导体（DODHT）_2PF_6的环境压力下通过X射线衍射和磁敏感性测量测量的绝缘阶段，绝缘体相是具有条纹类型电荷模式的电荷有序状态。此外，更精确地在压力下对该材料的运输特性进行测量，尤其是在……超导阶段和绝缘体阶段之间的边界更大，导致压力温度相图；在相图中，超过13 kbar的压力的超导和正常抗性状态在13.2至15.1 kbar之间的超导相上方存在。由于在高达8 kbar的运输测量中观察到了清晰的绝缘体过渡，因此电荷有序绝缘子可能会在至少8 kbar的高压区域扩散。这些结果表明，电荷波动可能对这种材料的超导性至关重要，目前的材料将视为一种简单的工具，用于投资超导性和电荷波动之间相互作用的宇宙。随着分子导体的研究，多功能超分子材料的开发及其对有机设备的多功能超级材料的开发，已计入有机设备。对于此类材料，新制备了供体 - 受体连接的分子，例如C_ <60> -TTF二元组，并且观察到明显的分子内电荷转移相互作用与先前报道的C_ <60> -TTF系统不同。通过对激发态的光物理研究，c_ <60> -TTF二元组的光诱导电荷分离状态的寿命非常短，这对于有机设备（例如有机太阳能电池）是不利的。为了克服这种情况，准备了C_ <60> -TTF树枝状聚合物，尽管效率低，但仍观察到太阳能电池性能。较少的

项目成果

Crystal structures and physical properties of new Ni complexes with dihydro-TTF dithiolate

新型镍与二氢-TTF二硫醇配合物的晶体结构和物理性质

• 发表时间: 2003
• 期刊: Synth.Met. 135-136
• 作者: K.Yokoyama;H.Nishikawa;K.Kikuchi;T.Kodama;I.Ikemoto;J.Yamada
• 通讯作者: J.Yamada

Structure and properties of radical salts of DODHT derivatives

DODHT衍生物自由基盐的结构和性质

• 发表时间: 2003
• 期刊: Synthetic Metals 137
• 作者: J.Yamada;H.Akutsu;H.Nishikawa;K.Kikuchi;H.Nishikawa et al.;M.Umemiya et al.;J.Yamada et al.;T.Kodama et al.;H.Nishikawa et al.;H.Nishikawa et al.;H.Nishikawa et al.
• 通讯作者: H.Nishikawa et al.

Crystal structure and physical properite of (DODHT)_2FeCl_4

(DODHT)_2FeCl_4的晶体结构和物理性质

• 期刊: Polyhedron (in press)
• 作者: H.Yoshino;K.Murata;K.Saito;H.Nishikawa;K.Kikuchi;I.Ikemoto;K.Masunaga et al.;H.Nishikawa et al.
• 通讯作者: H.Nishikawa et al.

A new organic superconductor, β(BDA-TTP)_2GaCl_4 [BDA-TTP=2,5-(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene]

一种新型有机超导体β(BDA-TTP)_2GaCl_4 [BDA-TTP=2,5-(1,3-二硫基-2-亚基)-1,3,4,6-四硫五环烯]

• 发表时间: 2003
• 期刊: Chem.Commun.
• 作者: J.Yamada;T.Toita;H.Akutsu;S.Nakatsuji;H.Nishikawa;I.Ikemoto;K.Kikuchi;E.S.Choi;D.Graf;J.S.Brooks
• 通讯作者: J.S.Brooks

Dihydro-TTFs and bis-fused 1,3-dithiol-2-ylidene donors, TTF chemistry - Fundamentals and applications of tetrathiafulvalene, Chapter 11

二氢-TTF 和双稠合 1,3-二硫醇-2-亚基供体，TTF 化学 - 四硫富瓦烯的基础知识和应用，第 11 章

• 发表时间: 2004
• 作者: H.Nishikawa;Y.Yasuda;T.Kodama;K.Kikuchi;I.Ikemoto;J.Yamada;H.Oshio;H.Nishikawa et al.;K.Masunaga et al.;R.Izumi et al.;J.Yamada et al.;J.Yamada et al.
• 通讯作者: J.Yamada et al.