基于环辛四烯的柔性有机半导体材料的设计、合成及性能研究

Organic semiconductors have been attracted more attention for over a decade because these materials can potentially be fabricated large-area and flexible organic electronic devices at very low cost. Organic semiconductors are composed of molecules with specific configurations. The orientation and packing modes of the molecules have great effect on the overall properties of the materials. In order to search high-ordered and high-performance semiconductors and overcome the difficulty of controllable self-assembly, V-shaped cyclooctatetraene (COT) framework, which is easy to form 1-D high-ordered stacking, was introduced into the rigid -conjugated systems. The flexible-rigid hybrid  system possesses good -stacked ability to form close  stacking. Most importantly, the flexible character of COT framework makes the molecule become real flexible. Our research will give theoretical and experimental support for exploring multifunctional semiconductor materials according to study the relationship between the molecular configuration and properties.

有机半导体材料由于其在柔性、大面积、低成本以及微/纳米电子器件中的潜在应用，备受科研工作者的关注。有机半导体由特定结构的分子基元构成，分子的取向和排布对其物理性质有重要的影响。为寻求结构规整、高度有序化、性能优异的有机半导体材料，克服常规有机半导体材料难于可控性组装的问题，我们拟以易于形成一维长程有序堆积的V-型环辛四烯骨架引入到刚性共轭体系中，保证共轭体系间形成密堆积的同时，环辛四烯骨架的柔性特征使有机分子具有动态性质，使材料做到真正意义上的柔性。期望通过系统研究其固态堆积及半导体性能之间的关系，为多功能性有机半导体材料的开发提供理论支持和实验依据。

我们设计并合成了一系列基于环辛四烯和其他骨架的有机功能性小分子。基于环辛四烯的功能性化合物的成功合成是我们后续开展相关半导体性质、自组装性质等研究的前提和保证。含有吡啶基团的Λ型分子可以用作pH荧光探针而离子型的有机-无机复合吡啶盐分子表现出聚集态荧光增强性质，其晶体结构是一个由一维的阴离子链贯穿于阳离子形成的二维网络结构中而形成的三维空间的网络互穿结构。有机功能性小分子在金属表面的研究表明端基炔溴分子在Au(111)表面可以发生脱卤耦合反应，并形成具有炔基骨架的二聚体、一维分子线以及二维网络结构，为制备具有炔基骨架的新颖半导体纳米材料提供了一种可能的路径；端基为氰基的V型分子在Cu(110)和Cu(100)表面可形成氢键链状或配位结构；功能化碱基A分子可以在Au(111)表面形成类DNA链结构。这些研究为功能性有机分子的设计和合成提供了较好的理论和实验参考价值。