多重螺烯类手性纳米碳分子的稠合式合成及其光电性质研究

Molecular nanocarbons have been one of the research frontiers in the field of organic functional materials. In recent years, a novel type of multi-helicene-based chiral nanocarbons has attracted broad research interest due to their intriguing properties. However, their syntheses have been of great challenge and further derivatizations have been very difficult; their optoelectronic devices have seldom been investigated and the chirality-related properties have never been exploited in devices. In this project, we will develop a novel synthetic strategy of annulative couplings to efficiently construct a series of chiral nanocarbon molecules by directly fusing the helicene moieties onto polycyclic aromatic hydrocarbons. This new approach is expected to provide a library of molecular nanocarbons for materials applications. Further, we will evaluate their charge mobilities by organic field-effect transistors, and select high-mobility molecules to investigate how different chiral isomers affect solid-state molecular arrangements, charge-carrier transport, and chiroptical properties. We will then use the chiral molecules to study their detecting behavior of circularly polarized light and reveal the structure-property relationship for guiding further molecular designs, and finally aim to achieve high-performance photodetectors for circularly polarized light.

纳米碳分子的设计、合成及性能研究是有机功能材料领域的前沿之一。近年来多重螺烯类手性纳米碳分子由于其独特的性质吸引了广泛的研究兴趣。然而，其合成颇具挑战性，衍生化仍然十分困难；其光电器件性质尚研究不足，尤其是其手性性质在光电器件中的应用尚未报道。本项目拟发展一种新颖的高效合成策略，通过“稠合式偶联”反应，直接在稠环芳烃基础上构建多重螺烯分子，从而以简捷的方式快速高效合成一系列手性纳米碳分子，建立结构丰富的材料分子库。在此基础上，开展其光电性质研究，筛选高电荷迁移率的分子，系统研究不同手性异构体与其分子排列、电荷输运机制及手性光学性质的内在关系；进而构建偏振光探测器件，研究不同手性分子对偏振光响应性质的影响，进一步为此类分子的理性设计提供理论指导，以期实现高性能手性光电器件的制备和应用。

多重螺烯类手性纳米碳分子具有独特的螺旋手性和光电性质，近年来吸引了广泛的研究兴趣。然而，如何实现该类分子的高效合成，以及分子结构如何影响手性光电性质，是该领域尚需解决的关键科学问题。本项目探索了包括稠合式偶联在内的多种合成方法，简捷高效构筑了一系列新颖的螺烯类共轭分子，包括基于全碳骨架的及杂原子掺杂的螺烯共轭分子体系；深入研究揭示了影响发光效率、不对称因子、电荷迁移率等性能参数的重要因素；在此基础上，通过分子理性设计，发展了具有高发光量子效率的基于苝螺旋拓展的手性纳米碳分子，以及具有高不对称因子、高电荷迁移率的硼氮杂螺烯类共轭分子材料，并构筑了圆偏振光探测器件，获得了出色的性能。本项目的研究成果为发展新型多重螺烯类手性有机光电材料提供了新的思路，共发表论文12篇，其中以通讯作者发表论文10篇，包括J. Am. Chem. Soc. 2篇，Angew. Chem. Int. Ed. 5篇，Adv. Sci. 1篇。