有机光电材料中分子pi-堆积的构筑及其对光电性能的影响

Search and design of the solid-state highly emissive organic materials with high carrier mobility has always been a difficult problem in the field of organic optoelectronics. Recently, a few reports reveal that some specific molecular stacking modes are beneficial for maintaining or even enhancing the solid-state emission. Meanwhile, the carrier transport capabilities are much dependent on the molecular stacking as well. This provides the possibility for exploring the organic optoelectronic materials with both solid-state emission and high carrier mobility by designing proper suparmolecular structures. In this project, to construct the partial intermolecular π-stacking, the supramolecular structure simulation and optoelectronic theoretical calculations are performed to help with designing and synthesizing a series of new arylbenzoxale- and arylspiro[fluorene-9',9'-xanthracene]-based solid-state highly emissive organic materials with high carrier mobility. By modern spectroscopic and Organic Field Effect Transistors or Time of Flight methods, the solid-state emissive behavior and carrier mobility of these materials will be investigated. The applications of these materials in some optoelectronic devices will be tried. On this experimental basis, we focus on investigating the structure-property relationship in essence at the supramolecular level－the impact of the molecular π-stacking on the micro dipole-dipole interactions, molecular photophysics, transfer integral, reorganization energy, and further on the macro solid-state emissive behavior and carrier mobility－by supramolecules preparation and theoretical calculations. This work can provide some theoretical and experimental basis for search of the practically valuable organic optoelectronic materials.

研究开发具有高载流子迁移率的有机固态发光材料，一直是有机光电子领域的一个难题。近年来有少量研究表明，在超分子层面某些特殊的分子堆积模式能够保持甚至促进固态发光，而分子堆积模式与电荷传输性能也密切相关，这就为从超分子角度寻找同时具有固态发光和较好电荷传输性能的有机光电材料提供了可能。本课题以构筑一定程度的分子π堆积为宗旨，结合超分子结构模拟及光电性能理论计算，设计合成一系列新型的具有高载流子迁移率的芳基苯并唑类以及芳基螺芴氧杂蒽类固态发光材料。通过现代光谱技术与有机场效应晶体管法、飞行时间法等技术研究其固态发光与载流子迁移性能，初步尝试其光电子器件应用。并结合超分子制备手段与相关理论计算方法，着重研究分子pi堆积对微观偶极-偶极作用、分子光物理、转移积分与重组能进而对宏观固态发光行为及载流子迁移性能的影响，研究其本质的构效关系，为寻找具有实际应用价值的有机光电子材料提供一定的理论和实验依据。

本项目主要在前期研究有机光功能材料固态发光性质的内在机制的基础上，设计了一系列兼具较好载流子传输性能和较好固态发光性质的有机电致发光材料与有机激光材料，详尽研究了材料的光物理行为与构效关系。另外，通过特殊的光物理或光化学性质，设计了系列具有优异性能的温度传感、压力传感及有机光/电材料。可通过光化学反应控制载流子陷阱深度来调控光电器件的载流子捕获和传输能力，进而实现光调控的多功能有机光电器件。在本项目的资助下，以第一作者或通讯作者在Advanced Materials、Advanced Functional Materials、Advanced Optical Materials、Advanced Electronic Materials、Chemical Communications、The Journal of Physical Chemistry C等期刊上发表学术论文21篇，申请专利8项，获得授权专利2项。上述成果为进一步设计新型光电材料提供理论和实验依据。