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

本课题的目的是研制一种新型的高分辨率固态核磁共振光谱仪，用于研究固体状态下有机分子的动力学行为。需要创新的主要工具性问题如下。(1)通过引入四相移相器和其他硬件，优化脉冲频率，以便进行CRAMPS（高分辨率固态1HNMR）实验。(2)通过改进探针的冷却系统，提高CP/MAS实验的变温下限。(3)制备光透射探头，以便在CP/MAS测量时照射样品。第一个问题成功地解决了。获得了马来酸和柠檬酸的高分辨率^1H核磁共振光谱，分辨率为0.32 ppm。对后两点提出了技术解决办法，但由于财政条件的原因，无法对工具进行修改。利用新型光谱仪，对固体样品进行了CP/MAS测量，以阐明有趣的动力学行为。典型研究如下：(1)研究具有对电和（反）铁电行为的b-羟基烯酮的固态互变异构化；(2)制备新的宿主分子，如双供体或熔融噻吩，并阐明包合物中客体分子的动力学行为。(3)制备带介生基团的光致二乙炔，并通过CP/MAS测量监测光致聚合。综上所述，利用新开发的高分辨率固体核磁共振光谱仪，揭示了有机分子在固体状态下的新的物理性质和化学反应，这些物理性质和化学反应来源于有机分子的动力学行为。

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.