Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Kyoto 615-8510, Japan.
Chemistry. 2012 Apr 2;18(14):4216-24. doi: 10.1002/chem.201103653. Epub 2012 Feb 28.
[2.2]Paracyclophane-based through-space conjugated oligomers and polymers were prepared, in which poly(p-arylene-ethynylene) (PAE) units were partially π-stacked and layered, and their properties in the ground state and excited state were investigated in detail. Electronic interactions among PAE units were effective through at least ten units in the ground state. Photoexcited energy transfer occurred from the stacked PAE units to the end-capping PAE moieties. The electrical conductivity of the polymers was estimated using the flash-photolysis time-resolved microwave conductivity (FP-TRMC) method and investigated together with time-dependent density functional theory (TD-DFT) calculations, showing that intramolecular charge carrier mobility through the stacked PAE units was a few tens of percentage larger than through the twisted PAE units.
[2.2]制备了基于并环芳烃的贯穿空间共轭寡聚物和聚合物，其中聚（对亚芳基乙炔）（PAE）单元部分π-堆叠和层叠，并详细研究了它们在基态和激发态下的性质。在基态中，PAE 单元之间的电子相互作用至少通过十个单元有效。从堆叠的 PAE 单元到端接的 PAE 部分发生光致能量转移。使用闪光光解时间分辨微波电导率（FP-TRMC）方法估算了聚合物的电导率，并与时间相关的密度泛函理论（TD-DFT）计算一起进行了研究，表明通过堆叠的 PAE 单元的分子内电荷载流子迁移率比通过扭曲的 PAE 单元的迁移率大几十百分点。
