Crystal structural change in poly(3-alkyl thiophene)s induced by iodine doping as studied by an organized combination of X-ray diffraction, infrared/Raman spectroscopy and computer simulation techniques
Crystal structural change in poly(3-alkyl thiophene)s induced by iodine doping as studied by an organized combination of X-ray diffraction, infrared/Raman spectroscopy and computer simulation techniques
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DOI：
10.1016/s0032-3861(96)00876-2
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发表时间：
1997-06
期刊：
影响因子：
4.6
通讯作者：
K. Tashiro;Masamichi Kobayashi;T. Kawai;K. Yoshino
中科院分区：
文献类型：
--
作者：
K. Tashiro;Masamichi Kobayashi;T. Kawai;K. Yoshino
利用x射线成像板和计算机模拟技术，记录了原始和碘掺杂聚（3-烷基噻吩）s[聚（3-己基噻吩）和聚（3-十二基噻吩）]结构分析的初步结果。原始聚合物的晶体结构被发现是由烷基并排排列而成的堆叠层组成，其中单层和双层结构都是可能的。研究发现，掺杂碘的聚（3-烷基噻吩）具有隧道结构，这种隧道结构是由聚合物链沿链轴沿重复周期的一半协同平移而产生的，其中多碘离子如I3 -和I5 -被捕获，与聚噻吩骨架链形成电荷转移配合物。通过构建能量最小化晶体结构模型来模拟这些结构变化，得到了与观测值接近的x射线纤维图。红外光谱和拉曼光谱在碘掺杂过程中发生了两个阶段的变化，提出了聚噻吩与碘离子结合形成极化子和双极化子的可能性。
Preliminary results of the structural analysis of pristine and iodine-doped poly(3-alkylthiophene)s [poly(3-hexylthiophene) and poly(3-dodecylthiophene)] have been recorded by utilizing an organized combination of X-ray imaging plate and computer simulation techniques. The crystal structure of the pristine polymers was found to be composed of stacked layers constructed by a side-by-side arrangement of alkyl groups, where both the single and double layer structures were possible. The iodine-doped poly(3-alkylthiophene)s have been found to possess a tunnel structure produced by a cooperative translation of the polymer chains along the chain axis by half the repeating period, into which polyiodide ions such as I3−and I5−were trapped to form a charge-transfer complex with polythiophene skeletal chains. These structural changes were simulated by constructing energetically minimized crystal structural models, which gave X-ray fibre diagrams close to those of the observed ones. The infrared and Raman spectra were found to change in two stages during iodine doping, and the possibility of polaron and bipolaron species constructed by a combination of polythiophene and iodine ions was proposed.