A series of conjugated polymers comprising polythiophene, polyselenophene, and polytellurophene with branched 3,7‐dimethyloctyl side chains, well‐matched molecular weight, dispersity, and regioregularity is synthesized. The ionization potential is found to vary from 5.14 to 5.32 eV, with polytellurophene having the lowest potential. Field‐effect transistors based on these materials exhibit distinct hole transport mobility that varies by nearly three orders of magnitude, with polytellurophene having the highest mobility (2.5 × 10⁻² cm² V⁻¹ s⁻¹). The large difference in mobility demonstrates the significant impact of heteroatom substitution. Although the series of polymers are very similar in structure, their solid‐state properties are different. While the thin film microstructure of polythiophene and polyselenophene is identical, polytellurophene reveals globular features in the film topography. Polytellurophenes also appear to be the least crystalline, even though their charge transport properties are superior to other samples. The torsional barrier and degree of planarity between repeat units increase as one moves down group‐16 elements. These studies show how a single atom in a polymer chain can have a substantial influence on the bulk properties of a material, and that heavy group‐16 atoms have a positive influence on charge transport properties when all other variables are kept unchanged.

中文翻译：

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聚噻吩的硒和碲类似物的自组织和电荷输运性质

合成了一系列共轭聚合物，包括具有支链3,7-二甲基辛基侧链，分子量，分散性和区域规则性良好匹配的聚噻吩，聚硒吩和聚碲烯。发现电离电势在5.14至5.32 eV之间变化，其中聚碲烯的电势最低。基于这些材料的场效应晶体管表现出不同的空穴传输迁移率近三个数量级的变化，与具有最高迁移率polytellurophene（2.5×10 ^-2平方厘米V ^-1小号^-1）。迁移率的巨大差异证明了杂原子取代的重大影响。尽管这一系列聚合物的结构非常相似，但它们的固态性质却有所不同。尽管聚噻吩和聚硒酚的薄膜微观结构是相同的，但聚tellurophene在膜形貌中显示出球形特征。聚二茂铁似乎也是结晶最少的，尽管它们的电荷传输性能优于其他样品。向下移动第16组元素时，重复单元之间的扭转势垒和平面度增加。这些研究表明，聚合物链中的单个原子如何对材料的整体性能产生重大影响，