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Development of optically detected magnetic resonance spectrometer and its application for characterization of π-conjugated polymers

光学检测磁共振波谱仪的研制及其在π共轭聚合物表征中的应用

基本信息

批准号：
12555265
负责人：
INOUE Yoshio
金额：
$ 4.99万
依托单位：
Tokyo Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2000
资助国家：
日本
起止时间：
2000 至 2001
项目状态：
已结题

项目摘要

In this research project, we developed a time-resolved optically detected magnetic resonance(ODMR) spectrometer at a zero or low magnetic field condition. A broadband reentrant cavity probe with a range of 250 MHz〜1.5 GHz were built.We have assembled a timing generator with 24 independent channels and 10 ns resolution. We make use of the timing generator for amplitude modulations and phase modulation of microwave pulses, and phase sensitive detection at the receiver. A xenon flash lamp with a selective wave length by optical filter was used as a light source. The phase-sensitive detected signals digitized by a digital storage oscilloscope were transferred to a computer via a general purpose interface bus(GPIB), and then averaged. We succeeded in developing the time resolved ODMR spectrometer system with connecting both the microwave and optical portions. We have made optically detected electron paramagnetic resonance(ODEPR) and optically detected nuclear magnetic quadrupolar resonance( … More ODNQR) measurements of 1,4-dibromonaphthalene (DBN), which is a model compounds to π-conjugated polymers.As a preliminary research, solid-state structure of some five-membered ring π-electron conjugated polymers with high regio-regularity was investigated by the ^<13>C and ^2H solid-state NMR. We performed ^<13>C cross polarization and magic-angle sample spinning (CPMAS) measurements of 99 % head-to-head poly(4-methylthiazole-2,5-diyl) (HH-P4MeTz) and 99 % head-to-head poly(3-methylthiophene-2,5-diyl) (HT-P3MeTh), which were synthesized by dehalogenative polycondensations with zero-valent nickel complexes. An analysis of principal components of chemical shielding tensor for the methyl carbon determined by the two-dimensional spin-echo measurements and ab initio MP2 chemical shielding calculation show that the backbone twist in highly correlated with the intramolecular methyl rotaion and that the two distinctive signals of the methyl carbons are attributed to the ordered and the quasi-ordered phases. Coexistence of the both phases were manifested by variable temperature ^2H quadrupolar NMR meansurements for methyl-deuterated HH-P4MeTz. It is noticeable that the quasi-ordered phase is observed even in polymers with the short side chain. Less

在本研究项目中，我们研制了一台零磁场或低磁场条件下的时间分辨光学检测磁共振(ODMR)光谱仪。研制了250 MHz~1.5 GHz的宽带可重入腔探头，并组装了24个独立通道、10 ns分辨率的时序发生器。我们利用时序发生器对微波脉冲进行幅度调制和相位调制，并在接收端进行相敏检测。光源采用滤光片可选择波长的氙灯。由数字存储示波器数字化的相敏检测信号通过通用接口总线(GPIB)传输到计算机，然后进行平均。将微波部分和光学部分连接起来，成功地研制出时间分辨的ODMR光谱仪系统。我们进行了光学探测电子顺磁共振(ODEPR)和光学探测核磁共振(…)作为一种π共轭聚合物的模型化合物，1，4-二溴代萘(DBN)的更多的ODNQR测量。作为一个初步的研究，用固体核磁共振研究了一些具有高区域规整性的五元环π-电子共轭聚合物的固态结构。采用交叉极化和魔角旋转(CPMAS)方法对零价镍配合物脱卤聚合法合成的99%聚(4-甲基噻唑-2，5-二基)(HH-P4MeTz)和99%(3-甲基噻吩基-2，5-二基)(HT-P3MeTh)进行了测试。由二维自旋回波测量和从头算MP2化学屏蔽计算确定的甲基碳化学屏蔽张量的主成分分析表明，甲基碳的主链扭曲与分子内的甲基旋转离子高度相关，甲基碳的两个明显信号属于有序和准有序相。用变温~2H四极核磁共振法测定了HH-P4MeTz的甲基化产物。值得注意的是，即使在侧链较短的聚合物中也能观察到准有序相。较少