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

本研究以1，6-二氨基芘（DAP）电荷转移配合物为研究对象，对其晶体结构和物理性质进行了系统的研究。选择了15种受体强度分布较广的电子受体与DAP形成联合收割机，根据其结构和电子状态可分为两大类：1.具有中性混叠结构的配合物：与对氯苯醌（CHL）的配合物属于第一类。该晶体包括中性施主和受主的混合堆叠柱。一般而言，这种晶体的导电性预期非常差。然而，已经发现，不仅与CHL，而且与对溴苯胺和2，5-二溴-3，6-二氯对苯醌的配合物显示出高的导电性。此外，还发现磁性铁镍合金的电导率和温度依赖性有两种可区分的趋势 ...更多信息 2.具有离子分离堆积结构的配合物：我们发现了五个新的具有类似于DAP-TCNQ的离子分离堆积结构的配合物，在所有的配合物中，组分分子都是完全电离的。电阻率很低，室温下为10^<-1>-10^3 Ω cm。然而，导电的激活能是非常大的。虽然分子间的面间距是均匀的，但由于振动模式的完全对称性，这两类分子可能是一个spin-Peierls系统，它们的共同特征是给体和受体之间存在氢键.由于导电的各向异性相当小，已经发现，它已被建议，氢键在他们不寻常的传输机制中起着重要的作用。由于缺乏一些结构性数据，系统比较尚未完成。在完成结构分析后，将对π电子系统之间的相互作用以及与氢键的关系进行系统的研究。少

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