Study on the Unusual Electrical Properties of Charge-Transfer Complexes with Intermolecular Hydrogen-Bonds

分子间氢键电荷转移配合物异常电学性质的研究

基本信息

批准号：
07454181
负责人：
INABE Tamotsu
金额：
$ 5.12万
依托单位：
HOKKAIDO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1997
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07454181/
关键词：
Charge-Transfer Complexes Hydrogen-Bonds 1.6-Diaminopyrene Electrical Conductivity

项目摘要

In this research project, systematic crystal growth of 1,6-diaminopyrene (DAP) charge-transfer complexes has been carried out to study on their crystal structures and physical properties. Fifteen electron acceptors, of which acceptor strength distributes in a wide renge, were selected to combine with DAP.These complexes can be categorized into two groups from their structure and electronic state, as follows.1. Complexes with Neutral Mixed-Stack Structure : The complex with p-chloranil (CHL) belongs to the first group. The crystal comprises mixed-stack columns of neutral donors and acceptors. In general, the electrical conductivity of such a crystal is expected to be very poor. However, it has been found that the complexes with not only CHL but also p-bromanil and 2,5-dibromo-3,6-dichloro-p-benzoquinone shows high conductivity. Furthermore, it has been found that there are two distinguishable trends in their electrical conductiviity and temperature dependence of the magnetic susceptibil … More ity.2. Complexes with Ionic Segregated-Stack Structure : We have found new five complexes which have ionic segregated-stack structure similar to DAP-TCNQ.In all the complexes, component molecules are completely ionized. The electrical resistivities are quite low ; 10^<-1>-10^3 OMEGA cm at room temperature. However, the activation energies of conduction are extremely large. Though the interplanar spacing between the molecules is uniform, they are suggested to be a spin-Peierls system, since totally symmetric vibrational modes have been observed.A common characteristic in these two groups is hydrogen-bonds between donors and acceptors. Since rather small anisotropy of the conduction has been found, it has been suggested that the hydrogen-bonding plays some important role in their unusual transport mechanism. Systematic comparison has not been complete due to lack of some structural data. The systematic study on the interaction between the pi-electron systems and the relation with the hydrogen-bonding will be performed after completion of the structure analyzes. Less

本研究项目对1,6-二氨基芘（DAP）电荷转移配合物进行了系统的晶体生长，研究了15种受主强度分布广泛的电子受体的晶体结构和物理性质。选择与DAP结合。这些配合物从其结构和电子态可以分为两类，如下： 1.具有中性混合堆叠结构的配合物：与对四氯苯醌（CHL）的配合物。属于第一组。该晶体包含中性供体和受体的混合堆叠柱。一般来说，这种晶体的电导率预计非常差，但是，已经发现，不仅含有CHL，而且含有CHL。对溴苯腈和2,5-二溴-3,6-二氯-对苯醌也表现出高电导率。此外，还发现它们的电导率和磁性的温度依赖性有两个明显的趋势。 2. 具有离子分离堆结构的配合物：我们发现了五种新的配合物，其具有类似于DAP-TCNQ的离子分离堆结构。在所有配合物中，组分分子完全电离，电阻率相当。低；室温下10^<-1>-10^3 OMEGA cm 然而，尽管分子之间的晶面间距非常大。由于观察到了完全对称的振动模式，因此它们被认为是自旋-佩尔斯系统。这两个组的共同特征是供体和受体之间的氢键，因为已经发现了相当小的传导各向异性，因此它是均匀的。由于一些结构数据的原因，氢键在其不寻常的传输机制中发挥着重要作用。结合意愿在结构嵌入完成后执行。