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

采用氢键连接的π电子系统设计功能固体

• 批准号: 02804032
• 负责人: INABE Tamotsu
• 金额: $ 1.09万
• 依托单位: Okazaki National Research Institutes
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02804032/
• 关键词: Intramolecular Hydrogen-bond; Charge-transfer complex; Hydrogen-bond structure; Proton dynamics; Intermolecular Hydrogen-bond

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

氢键系统，其中质子转移耦合的π电子构型的变化，是本研究的主题。如果分子之间的相互作用在结晶状态下足够强，则质子运动预计会调制晶体的电子性质。在本研究计划中，我们研究了分子内和分子间氢键体系的结构和物理性质，以探索基于质子转移构建新型功能固体的可能性.选择了N-水杨醛苯胺衍生物及其电荷转移配合物作为分子内氢键体系。通过对OH···N氢键结构的X射线分析，证实了质子的平衡位置因分子的化学修饰或分子间电荷转移相互作用的强度而改变。这种结构变化也可以从 ...更多信息 它们的热致变色行为和它们的红外光谱的差异。通过对^1H核磁共振弛豫时间的测量，我们发现质子动力学很大程度上取决于化学修饰引起的氢键结构变化。由于质子运动和传导电子之间的耦合有望导致一种新型的电性能，各种衍生物已被用作制备电荷转移复合物的供体组分。虽然还没有得到高导电性的单晶，但已经发现某些组合产生导电粉末。晶体生长的努力将继续下去。由芳香胺和TCNQ型或苯醌型受体组成的分子间氢键体系中的一些化合物已被发现是高导电的。然而，它们中的大多数具有混合型堆叠结构，这与典型的导体有很大不同。研究还发现，某些配合物可以通过热处理从非导电状态转变为导电状态。虽然DAP-TCNQ（DAP; 1，6-芘二胺），这是唯一的具有分离型堆积结构的配合物，已被发现在室温下显示出高的导电性，导电的活化能非常高。阐明这些独特现象与氢键之间的关系将是本研究的下一步。少

项目成果

K.Okaniwa他: "Intra-and Inter-Molecular Charge Transfer Interactions in H-Bonded DTPP Crystals" Molecular Crystals and Liquid Crystals.

K. Okaniwa 等人：“H 键合 DTPP 晶体中的分子内和分子间电荷转移相互作用”分子晶体和液晶。

S.Takeda他: "NMR Study of Proton Dynamics in the Hydrogen Bond in the Thermochromic Crystals of N-Salicylideneaniline Derivatives" Molecular Crystals and Liquid Crystals.

S. Takeda 等人：“N-水杨基苯胺衍生物热致变色晶体中氢键的质子动力学的核磁共振研究”分子晶体和液晶。

S.Takeda他: "NMR Study of Proton Dynamics in the NHO Hydrogen Bonds in the Thermochromic Crystals of N-Salicylideneanilines" Chemical Physics Letters. 189. 13-17 (1992)

S.Takeda 等人：“N-水杨基苯胺热致变色晶体中 NHO 氢键的质子动力学的 NMR 研究”《化学物理快报》189. 13-17 (1992)。

T. INABE, et al.: "Crystal Structure and Transport Properties of a Hydrogen-Bocnded 1:1 Charge-Transfer Complex Composed of 1,6-Pyrenediamine and 7,7,8,8-Tetracyanoquinodimethane (DAP-TCNQ)" manuscript.

T. INABE 等人：“由 1,6-芘二胺和 7,7,8,8-四氰基醌二甲烷 (DAP-TCNQ) 组成的氢结合 1:1 电荷转移复合物的晶体结构和传输特性”手稿

T.Inabe: "Proton Transfer in N-Salicylideneanilines.An Approach to Controlling the Charge Transport in Molecular Materials" New Journal of Chemistry. 15. 129-136 (1991)

T.Inabe：“N-水杨基苯胺中的质子转移。控制分子材料中电荷传输的方法”新化学杂志。