Electronic properties and reactivity of short-chain oligomers of 3,4-phenylenedioxythiophene (PheDOT).
Electronic properties and reactivity of short-chain oligomers of 3,4-phenylenedioxythiophene (PheDOT).
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DOI：
10.1002/chem.200501284
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发表时间：
2006-04
期刊：
影响因子：
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通讯作者：
I. F. Perepichka;Sophie Roquet;P. Leriche;J. Raimundo;P. Frère;J. Roncali
中科院分区：
文献类型：
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作者：
I. F. Perepichka;Sophie Roquet;P. Leriche;J. Raimundo;P. Frère;J. Roncali
已合成3,4-苯二氧噻吩（PheDOT）的二聚体和三聚体。与基于 3,4-乙撑二氧噻吩 (EDOT) 的母体系统不同，这些化合物在大气条件下非常稳定。二-和三-PheDOT 的电子吸收光谱表现出分辨率良好的电子振动精细结构，表明共轭结构通过非共价分子内硫-氧相互作用进行自刚性化。 PheDOT 低聚物与相应 EDOT 低聚物的紫外-可见光数据的比较表明，前者的 HOMO-LUMO 间隙随着链长的增加而减小得更快。循环伏安数据表明，虽然 PheDOT 的氧化电位低于 EDOT，但 PheDOT 二聚体和三聚体的氧化电位比基于 EDOT 的类似物高得多。对三种基于PheDOT的体系的电聚合的比较分析表明，虽然PheDOT很难聚合，但是其二聚体和三聚体可以很容易地电聚合。借助理论计算讨论了扩链时反应活性的意外增加。
The dimer and trimer of 3,4-phenylenedioxythiophene (PheDOT) have been synthesized. Unlike the parent systems based on 3,4-ethylenedioxythiophene (EDOT), these compounds are quite stable under atmospheric conditions. The electronic absorption spectra of di- and tri-PheDOT exhibit a well-resolved vibronic fine structure indicative of self-rigidification of the conjugated structure by noncovalent intramolecular sulfur-oxygen interactions. Comparison of UV-visible data for the PheDOT oligomers with those of the corresponding EDOT oligomers reveals a faster decrease of the HOMO-LUMO gap with chain length for the former. Cyclic voltammetric data show that whereas PheDOT oxidizes at a lower potential than EDOT, the PheDOT dimer and trimer exhibit much higher oxidation potentials than their EDOT-based analogues. A comparative analysis of the electropolymerization of the three PheDOT-based systems shows that although PheDOT is very difficult to polymerize, its dimer and trimer can be readily electropolymerized. This unexpected increase of reactivity with chain extension is discussed with the aid of theoretical calculations.