氟代对BDOPV系列小分子排列的精细调控-国家级大学生创新创业.PDF

氟代对 BDOPV 系列小分子排列的精细调控 北京大学 俞之奡 （北京大学化学与分子工程学院，北京市 100871 ）1 （Journal of the American Chemical Society , 2015, 137, 15947. 和 Advanced Materials , 2015, 27, 8015. ） 裴坚教授，王婕妤副教授 中文摘要：有机小分子单晶中的分子排列会极大地影响电荷传输性质，但由于分子间作用的复杂性，一般很难对单晶排 列进行精准调控。而在本篇工作中，笔者在五个 BDOPV 有机半导体小分子骨架的不同位置上引入不同数量的氟原子，实现 了对单晶中分子排列的精细调控。在单晶中，这些氟代 BDOPV 小分子的分子间距离以及分子间位错受到了氟原子位置和数 量的精细调控，从而单晶排列出现可控的变化。进一步的密度泛函理论计算标明氟原子引入导致的分子静电势不同是引起分 子排列不同的重要原因。此外，这五种小分子单晶的电子迁移率与最低未占有轨道（LUMO ）能级并不完全匹配，也证明了 分子排列对于其性能的重要影响。本工作不仅开发了一系列高电子迁移率的有机半导体，而且还为精细调控单晶中的分子排 列提供了一种设计策略，即氟代。 英文摘要：Molecular packing in organic single crystals greatly influences their charge transport properties but can hardly be predicted and designed because of the complex intermolecular interactions. In this work, we have realized systematic fine-tuning of the single-crystal molecular packing of five BDOPV-based small molecules through incorporation of fluorine atoms on the BDOPV backbone. While these molecules all exhibit similar column stacking configurations in their single crystals, the intermolecular displacements and distances can be substantially modified by tuning of the amounts and the positions of the substituent fluorine atoms. Density functional theory calculations showed that the subtle differences in charge distribution or electrostatic potential induced by different fluorine substitutions play an important role in regulating the molecular packing of the BDOPV compounds. In addition, the electron mobility of the five molecules did not show a good correlation with the LUMO levels, indicating that the distinct difference in charge transport properties is a result of the molecular packing. Our work not only provides a series of high-ele