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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

基本信息

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

项目摘要

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

在本研究项目中，基于新的分子设计，开发了新的有机导体和超导体，即稳定的分子金属的失稳，如TTP(四硫富瓦烯)和TTP(四硫戊烯)导体。为此，我们设计并合成了新的π-电子给体，其π-电子体系比以往的TTf和TTP给体都要少。研究了由这些π还原的电子给体制备的导电自由基盐的结构和物理性质，发现了一种新的超导体(DODHT)_2BF_4·H_2O。通过X射线衍射和磁化率测量研究了压力感生超导体(DODHT)_2PF_6的常压绝缘相，结果表明：(DODHT)_2PF_6的绝缘相是具有条状电荷图案的电荷有序态。此外，更精确地测量这种材料在压力下的传输特性，特别是在…附近在压力-温度相图中，在13kbar压力以上，超导相和正常电阻态共存，在13.2~15.1kbar压力范围内，绝缘体相直接存在于超导相上方。由于在高达8kbar的输运测量中观察到了明显的绝缘子转变，因此电荷有序绝缘子可能至少扩展到8kbar的高压区。这些结果表明，电荷涨落可能是这种材料中超导电性的关键，本材料将成为研究超导电性和电荷涨落相互作用普遍性的简单工具。通过对分子导体的研究，开展了多功能超分子材料的开发及其在有机器件中的应用。对于这类材料，新合成了给体-受体连接的分子，如C&lt；60&gt；-TTf二元体，并且观察到了与以前报道的C&lt；60&gt；-TTf体系不同的分子内电荷转移相互作用。通过对激发态的光物理研究发现，C&lt；60&GT；-TTF光诱导电荷分离态的寿命极短，这对有机太阳能电池等有机器件是不利的。为了克服这种情况，我们合成了C&lt；60-TTf树枝状大分子，尽管效率较低，但仍观察到了太阳电池的性能。较少

项目成果

期刊论文数量（64）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

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]

DOI：
发表时间：
2003
期刊：
Chem.Commun.
影响因子：
0
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

Crystal structure and physical properite of (DODHT)_2FeCl_4

(DODHT)_2FeCl_4的晶体结构和物理性质

DOI：
发表时间：
期刊：
Polyhedron (in press)
影响因子：
0
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.

Photophysical Study of New Methanofullerene-TTF Dyads : An Obvious Intramolecular Charge Transfer in the Ground States.

新型亚甲基富勒烯-TTF 二元组的光物理研究：基态下明显的分子内电荷转移。

DOI：
发表时间：
2004
期刊：
J.Phys.Chem. A108(11)
影响因子：
0
作者：
H.Nishikawa;Y.Sato;K.Kikuchi;T.Kodama;I.Ikemoto;J.Yamada;H.Oshio;R.Kondo;S.Kagoshima;J.Yamada;J.Yamada;T.Mori;J.Yamada;J.Yamada;E.S.Choi;H.Imai;Y.Oshima;H.Nishikawa
通讯作者：
H.Nishikawa

Structure and properties of radical salts of DODHT derivatives

DODHT衍生物自由基盐的结构和性质

DOI：
发表时间：
2003
期刊：
Synthetic Metals 137
影响因子：
0
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 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