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Development of novel physical properties derived from proton-dynamics in hydrogen-bonded molecular crystals

氢键分子晶体中质子动力学衍生的新物理性质的发展

基本信息

批准号：
02453006
负责人：
SUGAWARA Tadashi
金额：
$ 3.97万
依托单位：
University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1990
资助国家：
日本
起止时间：
1990 至 1992
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-02453006/
关键词：
Proton dynamics Dielectric property Tautomerization Phase transition X-ray crystallographic analysis Solid state high resolution NMR Dielectric constant measurement 分子間水素結合

项目摘要

This project aims at developing novel physical properties derived from proton dynamics in hydrogen bonded molecular crystals. There are two main topics to be investigated.1. Elucidation of mechanism of dielectric property derived from tautomerization of beta-hydroxyenones.Hydrogen bond patterns of 3-hydroxyenones, such as 3- or 9-hydroxy phenalenones were determined by X-ray crystallographic analysis and the possibility of tautomerization of these compounds in the crystalline state were investigated by high resolution solid state ^<13>C NMR (CP/MAS) measurements.(1) The SHG active crystal of 3-hydroxyphenalenone was obtained. Hydroxyenone forms a one-dimensional hydrogen-bonded array with short O-O distances (2.58A^^ﾟ).(2) Paraelectric behavior of 2-carboxy-3-hydroxyphenalenone was discovered by dielectric constant measurements. The crystal exhibits antiferroelectric transition at 40K. The switching rate of dipole moment is faster than 10GHz.(3) The disordered crystal structure of 9-hydroxyphenalenone (Phase II 255-280K) was found to be derived from a dynamic origin based on CP/MAS and dielectric measurements. The molecule undergoes not only a rapid tautomerization but also a 120ﾟ jumping motion in crystals and exhibits a paramagnetic behavior.2. Static and dynamic modulation of hydrogen bonds upon the transport property of molecular conductors.Ni(dmit)_2 complexes involving various counter ion systems connected by hydrogen bonds were prepared. Among them, temperature dependence of conductivity of the Ni(dmit)_2 complex carrying H_3O^+-H_2O-CH_3CN as a counter ion system exhibits a hystereses in the temperature range between 230 and 300K. The anomaly may be explained in terms of the dynamical disturbance caused by supercooled water molecules and oxonium ions which melt in this temperature range. The phenomenon may lead to a novel methodology of controlling physical properties based on dynamic processes which take place in the solid state.

该项目的目的是开发新的物理性质来自质子动力学的氢键分子晶体。有两个主要的主题要研究。1.β-羟基烯酮互变异构介电性能机理的阐明：通过X射线晶体学分析确定了3-羟基烯酮（如3-或9-羟基非那烯酮）的氢键模式，并通过高分辨固体~ 1C NMR（CP/MAS）测量研究了这些化合物在结晶状态下互变异构的可能<13>性。(1)获得了3-羟基非那烯酮的倍频活性晶体。羟基烯酮形成一维氢键阵列，具有短的O-O距离（2.58 A ^^π）。(2)通过介电常数的测量发现了2-羧基-3-羟基非那烯酮的顺电行为。该晶体在40 K时表现出反铁电转变。偶极矩的开关速率大于10 GHz。(3)9-羟基非那烯酮（Phase II 255- 280 K）的无序晶体结构被发现来自基于CP/MAS和介电测量的动态起源。该分子不仅发生快速的互变异构化，而且在晶体中发生120 μ m的跳跃运动，表现出顺磁性.氢键对分子导体输运性质的静态和动态调控制备了由氢键连接的不同抗衡离子体系组成的Ni（dmit）_2配合物。其中，Ni（dmit）_2配合物负载H_3O^+-H_2 O-CH_3CN反离子体系的电导率在230 ~ 300 K范围内随温度的变化关系为负相关。这种异常现象可以用过冷水分子和氧鎓离子在此温度范围内熔化所引起的动力学扰动来解释。这一现象可能导致一种新的方法来控制物理性能的基础上发生在固态的动态过程。