芳香轴烯大环的制备和环化：聚集诱导发光和孔状规整的碳纳米片

Shape-persistent, conjugated macrocycles have attracted continuous attentions because of their synthetic challenges, fantastic topologies, unique self-assembly behaviors as well as optical electronic properties, such as radialenes which contain star-like rings of radiating C=C bonds. Unfortunately, the high synthetic difficulty, instability and poor pi-conjugation of radialenes restrict their potential applications in functional organic electronics. Here we present the rational design, synthesis and characterization of a new type of radialene derivative (Aryl-expanded Radialene), where the aryl groups are inserted as the internal bridges. The introduction of aryl groups will enhance the conjugation of the whole macrocyclic molecule which is the basic requirement for organic electronic properties. The scope of aryl-expanded radialenes can be easily extended by varying the aryl groups from phenyl to heterocycles. Employed the hole in the radialenes, few possible carbon holey-nanosheets with well-defined structure may be afforded stepwise through selective oxidation coupling. Several attractive aspects including optical electronic property, aggregation-induced emission, supramolecular self-assembly and ion recognition, as well as structure-property relationship can be investigated thoroughly to put forth the aryl-expanded radialene as a novel building block for the organic electronic materials.

轴烯是一类拥有鲜明结构特征和广泛应用潜质的芳香大环，但其较高的合成难度、较差的稳定性和共轭程度限制了它在有机光电材料领域的应用。本项目拟设计、合成、表征一类使用芳香结构充当桥联的轴烯大环体系，并通过可控环化制备孔状规整的碳纳米片。项目期望通过芳香结构的引入增加轴烯大环的电子离域能力，改善其共轭程度，实现对光电性能的的开发和调控；通过从苯环到噻吩、吡咯等杂环的变化，丰富轴烯大环的结构多样性，满足功能开发的结构需求；通过可控分步环化获取结构规整的孔状碳纳米片，深入研究其构效关系。项目旨在完成芳香轴烯大环的光电性质的开发，聚集诱导发光性能的利用、超分子体系的自组装和离子识别的研究、构效关系的探索之后，使其发展成为一类具有特色的新型有机光电材料结构基元。

轴烯是一类拥有鲜明结构特征和广泛应用潜质的芳香大环，但其较高的合成难度、较差的稳定性和共轭程度限制了它在有机光电材料领域的应用。本项目通过探索芳香轴烯大环的合成路线，可以一次合成系列芳香轴烯大环衍生物。并且通过杂环的引入，进一步扩展芳香轴烯体系结构。首次将芳香基团引入到轴烯内部环结构中，以提高轴烯分子整体共轭程度，增加电子离域能力，改善传统轴烯母体和三键类轴烯衍生物的共轭程度。通过研究芳香轴烯大环的聚集诱导发光特性、超分子组装和识别能力、光电器件性能，系统挖掘轴烯类衍生物在有机光电材料方面的潜在用途。并通过认知其材料结构-性能的关系为后续发展提供理论指导。综上，本项目通过分子结构设计、合成路线筛选、发光性能和组装行为表征，获取了一类使用芳香结构充当桥联的轴烯大环体系，报道一类具有特色的全新大环体系并研究其光电性质，并初步尝试了可控环化制备孔状规整的碳纳米片。围绕这一课题方向，相关成果在国际重要期刊上发表论文数篇，整体水平已达国际领先水平。目前已发表相关学术论文SCI论文9篇，期中包括多篇本领域国际主流杂志等，申请国家发明专利1项。