The importance of intramolecular conductivity in three dimensional molecular solids
The importance of intramolecular conductivity in three dimensional molecular solids
复制标题
DOI：
10.1039/c9sc03144h
复制
发表时间：
2019-10-28
期刊：
影响因子：
8.4
通讯作者：
Steigerwald, Michael L.
中科院分区：
文献类型：
--
作者：
Ball, Melissa L.;Zhang, Boyuan;Steigerwald, Michael L.
近年来，人们对有机场效应晶体管的分子结构和功能之间的关系的理解取得了巨大的进展。已知当分子间相互作用强且分子内重组能低时，以迁移率和开/关比为特征的有机场效应晶体管的度量得到增强。虽然当描述具有简单和平面芳族分子组分的有机场效应晶体管时，这些要求是足够的，但是它们不足以用于复杂的结构单元，其具有将载流子定位在分子上的潜力。在这里，我们表明，分子内导电性可以发挥作用，在控制器件特性的有机场效应晶体管与大环积木。我们使用两个异构的大环半导体，由联二噻吩和联二萘嵌苯二酰亚胺，发现反式连接的大环具有更高的流动性比顺式为基础的设备。通过组合的单分子结电导测量的大环化合物的组分，控制实验与无环对应物的大环化合物，和分析的每一种材料，使用光谱学，电化学，和密度泛函理论，我们属性的差异，在电子迁移率的OFFEs创建的两个异构体的两个大环化合物的分子内导电性的差异。
Recent years have seen tremendous progress towards understanding the relation between the molecular structure and function of organic field effect transistors. The metrics for organic field effect transistors, which are characterized by mobility and the on/off ratio, are known to be enhanced when the intermolecular interaction is strong and the intramolecular reorganization energy is low. While these requirements are adequate when describing organic field effect transistors with simple and planar aromatic molecular components, they are insufficient for complex building blocks, which have the potential to localize a carrier on the molecule. Here, we show that intramolecular conductivity can play a role in controlling device characteristics of organic field effect transistors made with macrocycle building blocks. We use two isomeric macrocyclic semiconductors that consist of perylene diimides linked with bithiophenes and find that the trans-linked macrocycle has a higher mobility than the cis-based device. Through a combination of single molecule junction conductance measurements of the components of the macrocycles, control experiments with acyclic counterparts to the macrocycles, and analyses of each of the materials using spectroscopy, electrochemistry, and density functional theory, we attribute the difference in electron mobility of the OFETs created with the two isomers to the difference in intramolecular conductivity of the two macrocycles.