Development of a high resolution solid-steate NMR spectrometer and investigation dynamical behavior of organic molecules in the solid state.

开发高分辨率固态核磁共振波谱仪并研究固态有机分子的动力学行为。

• 批准号: 02554016
• 负责人: SUGAWARA Tadashi
• 金额: $ 12.16万
• 依托单位: University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental 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/grant/KAKENHI-PROJECT-02554016/
• 关键词: Solid-state high resolution NMR; Dynamical behavior of organic molecules in the solid state; Tautomerization in the solid state; Polymerization in the solid state; Polydiacetylene; beta-Hydroxyphenalenone; ヒドロキシフェナレノン; 固体高分解能核磁気共鳴装置; パルス系列; 光透過プロ

The purpose of the project is to produce a new type of a high resolution solid-state NMR spectrometer for investigating dynamical behavior of organic molecules in the solid state.1. The main instrumental problems to be innovated are as follows.(1) Optimize pulse frequencies in order to perform CRAMPS experiments (high resolution solid state ^1HNMR) by introducing a four-phase shifter and other hardwares.(2) Improve a lower limit of variable temperatures for CP/MAS experiments by modifying a cooling system of the probe.(3) Prepare a photo-transmission probe in order to irradiate a sample during CP/MAS measurements.The first problem was successfully solved. High resolution ^1H NMR spectra of maleic acid and citric acid were obtained with a resolution of 0.32 ppm. Technical solutions concerning to the latter two points were proposed, although instrumental modifications could not be achieved due to the financial condition.2. Utilizing the novel spectrometer, CP/MAS measurement were performed on solid samples to elucidate intriguing dynamical behaviors. Typical studies are as follows.(1) Investigate the solid state tautomerization of b-hydroxyenones which exhibit paraelectric and (anti)ferroelectric behaviors(2) Prepare new host molecules such as twin-donors or fused thiophenes and elucidate dynamical behaviors of guest molecules in inclusion complexes.(3) Prepare photolabile diacetylenes carrying a mesogenic group and monitor the photo-induced polymerization by CP/MAS measurements.In summery, novel physical properties and chemical reactions, which are derived from a dynamical behavior of organic molecules in the solid state, have been elucidated by using the newly developed high resolution solid state NMR spectrometer.

本项目的目的是研制一种新型的高分辨率固体核磁共振光谱仪，用于研究有机分子在固体中的动力学行为。需要改进的主要仪器问题如下：(1)通过引入四相移器等硬件，优化脉冲频率以进行抽运实验(高分辨率固态)。(2)通过改进探头的冷却系统，提高CP/MAS实验的变温下限。(3)制备透光探头，用于CP/MAS测量过程中对样品的照射。第一个问题成功地解决了。获得了顺丁烯二酸和柠檬酸的高分辨~1H核磁共振谱，分辨率为0.32ppm。提出了与后两点有关的技术解决方案，但由于财政条件的原因，无法对工具进行修改。利用该新型光谱仪，对固体样品进行了CP/MAS测量，以阐明有趣的动力学行为。主要研究内容如下：(1)研究具有顺电和(反)铁电行为的对-羟基酮类化合物的固态互变异构化反应；(2)制备新型主体分子，如双给电子体或稠合的噻吩类分子，阐明客体分子在包合物中的动力学行为。(3)制备具有介晶基团的耐光性二乙炔，并通过CP/MAS测量监测光诱导聚合反应。综上所述，利用最新研制的高分辨率固体核磁共振波谱仪，揭示了有机分子在固体中的动力学行为所产生的新的物理性质和化学反应。

项目成果

H.SATO: "Monte Carlo Simmulation for the Interactions of Metal Complexes with the Silicate Sheets of a Clay" J.Am.Chem.Soc.114. 9382-9287 (1992)

H.SATO：“金属配合物与粘土硅酸盐片相互作用的蒙特卡罗模拟”J.Am.Chem.Soc.114。

菅原 正: "大橋裕二編〔分子性結晶の反応〕27.配向制御部位を有するジアセチレンの固相液晶相重合反応の解析" Realize.Inc., 10P (1992)

菅原正：“大桥裕二（编辑）[分子晶体中的反应]27.具有取向控制位点的丁二炔的固相液晶相聚合反应的分析”Realize.Inc.，10P（1992）

T. Okuno et al.: "Crystal Structure and Solid State Reactivity of Unsymmetrically Aryl-Substituted Diacetylene" Mol. Cryst. Liq. Cryst.225. 201-205 (1993)

T. Okuno 等人：“不对称芳基取代的二乙炔的晶体结构和固态反应性”Mol。

T.mochida: "Crystal Structure of 2-Carboxy-3-hyclroxydiben30tropne;Tautomeric System with an Extremely Short Intramolecular 0…0 Distance" Bull.Chem.Soc.Jpn.

T.mochida：“2-Carboxy-3-hyclroxydiben30tropne 的晶体结构；具有极短分子内 0…0 距离的互变异构系统”Bull.Chem.Soc.Jpn。

T.mochida: "Reconetraction of Hydrogen-Bonded Crystals of 3-Hydroxydiben30tropone Fomed by Solid State Decarboxylation of 2-Carboxy Derivative" Chem.Lett.

T.mochida：“通过 2-羧基衍生物的固态脱羧形成的 3-Hydroxydiben30tropone 氢键晶体的再聚合”Chem.Lett。