Design of functional solids employing pi-electron systems connected with hydrogen-bonds

在氢键系统中，质子转移与pi-electron配置性变化结合在一起，是本研究的主题。如果分子之间的相互作用在晶体管状态下足够强，那么质子运动就可以期望调制晶体管的电子性质。在这个研究项目中，对内部和分子间氢键系统的结构和物理特性进行了调查，以探索基于质子转移器的新型功能固体的可能性。N-盐酰亚胺衍生物及其电荷转移复合体已被选定为内聚氢键合系统。从OH. N氢键结构的X射线分析中，它被确认为质子变化的equilibrium位置由分子的化学修饰或由分子之间的电荷转移相互作用作用的强度。这一结构性变化也可以从该报告中得到证实。 ... More 他们的热致变色行为的差异和他们的红外光谱。从核磁共振放松时间的测量到^1H，质子动力学已经发现，由于化学修饰，氢键中的结构变化有很强的根据。自从质子运动和作用电子之间的耦合被期望产生一种新颖类型的电子性能，各种衍生物被用作捐赠者组件来准备电荷转移复合体。Although no highly conducting single crystals have been obtained yet， it has found that some combinations yield conducting powder。为水晶的增长而努力将继续下去。一些属于间分子氢键系统的化合物，由芳香胺和TCNQ型或苯唑喹酮型接受剂组成，已经找到了具有较高性能的化合物。However，大多数它们都有混合型堆叠结构，它们与类型导体有明显的区别。它还发现了一些复杂性，因为它们可以从非行为转化为由热治疗引起的状态。Although DAP-TCNQ（DAP）1，6-吡啶二胺），哪一种是唯一的复合体，它有一种隔离型堆叠结构，找到了在房间温度上显示出很高的行为能力，所述行为的激活能量是异常高的。在这些独特的现象之间发现了一种关系，而氢键将是这项研究的下一步。Less（低）

Hydrogen-bonded systems, in which the proton transfer is coupled with the pi-electron configurational change, are the subject of this study. If the interaction between the molecules is sufficiently strong in the crystalline state, the proton motion is expected to modulate the electronic properties of the crystal. In this research project, structures and physical properties of intra-and inter-molecular hydrogen-bonded systems have been investigated to explore the possibilities of constructing novel functional solids based on the proton transfer.1. N-Salicylideneaniline derivatives and their charge transfer complexes have been selected for the intramolecular hydrogen-bonded system. From X-ray analyses of the OH・・・N hydrogen-bond structures, it has been confirmed that the equilibrium position of the proton changes by chemical modification of the molecule or by the strength of the charge-transfer interaction operating between molecules. This structural change can also be verified from the … More differences in their thermochromic behavior and in their infrared spectra. From the measurements of the NMR relaxation time of^1H, the proton dynamics has been found to depend strongly on the structural change in the hydrogen bond by chemical modification. Since the coupling between the proton motion and conduction electrons is expected to lead a novel type of electrical properties, various derivatives have been employed as a donor component for preparing charge transfer complexes. Although no highly conducting single crystals have been obtained yet, it has been found that some combinations yield conducting powder. Efforts for the crystal growth will be continued.2. Some compounds which belong to the intermolecular hydrogen-bonded system, which are composed of aromatic amines and TCNQ type or benzoquinone type acceptors, have been found to be highly conducting. However, most of them have a mixed-type stacking structure, which is quite different from typical conductors. It has also been found that some complexes can be converted from non-conducting to conducting state by heat treatment. Although DAP-TCNQ(DAP; 1,6-pyrenediamine), which is the only complex which has a segregated-type stacking structure, has been found to show high conductivity at room temperature, the activation energy of conduction is anomalously high. Elucidation of the relation between these unique phenomena found and the hydrogen-bonding will be the next step of this study. Less