超分子共晶发光材料的制备及其性能研究

Supramolecular luminescent co-crystals not only have the intrinsic properties of each component but also show a variety of novel optoelectronic properties through unique packing structure, aggregate state and cooperative effect of multi component, and the relevant research is at the cutting edge of modern science. The challenges still remain that co-crystals often show quite low solid state luminescent efficiency, and the aggregate structures is difficult to manipulate and optimize. Therefore, we propose that supramolecular luminescent co-crystals were fabricated by introducing aggregation-induced emission luminophor served as the mainly luminescent component. Simultaneously, self-assembly will be taken to manipulate and optimize the aggregate structure, and eventually understanding the relationship between structure and properties as the view of molecular and supramolecular levels. This is of great importance to explore efficient supramolecular luminescent co-crystals in the field of organic solid state laser and develop controlled fabrication technique of co-crystal materials with promising prospect in applications.

超分子共晶发光材料因其特殊的分子堆积方式和聚集态结构以及不同组分之间的协同效应，使其不仅保留单一组分的固有性质，而且展现出更多新颖的宏观光电特性，已成为国际上研究的前沿热点。针对超分子共晶发光材料研究中所面临的固态发光效率低、聚集态结构难以调控等关键问题，本项目希望充分发挥聚集诱导发光分子在高效固态发光方面的潜力，利用自组装手段实现对聚集态的有效调控，制备高效发光超分子晶体材料，阐明分子结构、聚集态结构与发光性能之间的关系，探索超分子共晶发光材料在有机固体激光方面的应用，开发具有重要应用前景的超分子共晶发光材料及可控制备技术。

超分子共晶因其种类多样化、制备简单、独特分子堆积方式和新颖的光电功能等优势备受人们瞩目。然而，如何提高超分子共晶的发光性能，深入理解和调控超分子共晶组分间相互作用方面仍面临挑战。本项目率先以聚集诱导发光分子为发光主体，合理匹配客体分子，利用分子间氢键、卤键、π-π相互作用以及电荷转移相互作用等成功地构筑了系列高效发光超分子共晶材料，解决了共晶材料固态发光效率低的难题。系统考察了分子间相互作用影响聚集态结构的作用机制，揭示了聚集态结构演变和发光特性变化之间的内在联系，丰富了超分子共晶功能性起源的认知，为设计和理解超分子共晶材料奠定了良好的基础。值得一提的是，我们率先利用原位高压光谱技术揭示了超分子多组分共晶材料在外界刺激下聚集态结构演变和发光特性之间的关系，为理解不同刺激响应发光的作用机制提供了理论依据。并在溶剂挥发或热刺激诱导下可以从氢键/卤键主导的晶相I到π-π相互作用主导的晶相II的晶相转变，这一发现为理解外界刺激对聚集态结构的作用机制以及对发光特性的影响提供了新思路。此外，通过选取具有高效发光的主体分子，构筑了由π-π相互作用主导和氢键主导的多晶相共晶材料，并发现具有层状分隔柱堆积的二维共晶材料表现出各向异性的光波导和偏振特性，为设计高性能超分子共晶材料提供实验依据。项目执行期间，发表高水平SCI论文24篇，授权中国发明专利2项。