杂环稠合苝酰亚胺分子及其液晶高分子的自组装、聚集态结构和光学性质研究

Perylene diimide (PDI) derivative is a kind of important organic optoelectronic material. Despite its promising prospect, the photoelectric performance of the traditional PDI derivative is still challenging: the nonlinear optical property and its application is greatly restricted for the simplex energy-level structure; moreover, the luminous efficiency in the solid state will decrease significantly due to the fluorescence quenching. Heterocyclic annelated PDI derivative has novel energy-level structure and special self-assemble ability, which provides new opportunity to improve the nonlinear optical performance and luminous efficiency of the material. In this proposal, we intend to realize the designed optical property based on the self-assemble of the heterocyclic annelated PDI small molecules. Moreover, we will introduce the heterocyclic annelated PDI into polymer system as a liquid crystalline mesogen, to synthesize a new class of side-chain liquid crystalline polymer with high luminous efficiency and novel nonlinear optical property. The self-assemble, phase behavior, and aggregated structure of the materials will be studied. Their nonlinear optical property for different pulse laser and the luminous efficiency in the solid state and in solution will also be investigated. Based on these results, we will elucidate the relationship between the aggregated structure and optical property of the heterocyclic annelated PDI materials. This research will pave the way to the preparation of organic functional materials with special supermolecular structure and novel optical property by applying theoretical and experimental results, which has important scientific significance and application value.

苝酰亚胺（PDI）是一类重要的有机光电材料，但是，传统PDI衍生物在光学性能方面面临巨大挑战：单一的能级结构使其非线性光学性质及应用受到了很大限制；荧光淬灭效应还将导致材料本体发光效率的急剧下降。杂环稠合PDI分子具有新颖的能级结构和特殊的自组装能力，这为实现PDI材料发光效率和非线性光学性能的突破提供了机遇。本项目拟通过对杂环稠合PDI分子自组装行为的调控实现其特定的光学性质，并将其作为液晶基元引入到聚合物体系，制备一类具有高发光效率和新型非线性光学性能的侧链型液晶高分子。进而研究这些杂环稠合PDI小分子及高分子的自组装、相行为和聚集态结构，考察材料在溶液和本体状态下的发光效率，探讨其在各种脉冲激光下的非线性学性质。在此基础上，阐明聚集态结构与光学性质的内在联系。本项目将为具有特殊超分子结构和新型光学性质的有机功能材料的制备提供理论及实验依据，具有重要的科学意义和应用价值。

苝酰亚胺是一类重要的有机光电材料，但传统苝酰亚胺衍生物在光学性能方面面临巨大挑战。例如，荧光淬灭效应将导致该类材料本体发光效率的急剧下降。我们设计并合成了具有不同取代基的苝酰亚胺小分子及聚合物，并详细考察了这些材料的自组装、相行为和聚集态结构，研究了它们在溶液和本体状态下的光学性质。在此基础上，阐明了材料聚集态结构与光学性质的内在联系。研究结果表明，由于聚硅倍半氧烷的位阻作用，带有聚硅倍半氧烷取代基的杂环稠合苝酰亚胺分子可以形成特殊的离散晶体结构，从而有效地抑制荧光淬灭效应，因此在溶液和本体中都具有很高的发光效率。并且，由于具有电子转移和硅氧键断裂的双重检测机制，杂环稠合苝酰亚胺分子可以快速并选择性地检测氟离子，在发光器件和荧光探针方面具有潜在的应用价值。同样由于聚硅倍半氧烷的位阻作用，带有聚硅倍半氧烷取代基的侧链型苝酰亚胺聚合物可以形成特殊的柱状液晶结构。此外，将带有聚硅倍半氧烷取代基的苝酰亚胺分子引入聚合物荧光微球，同样可以有效地抑制荧光淬灭效应，从而提高聚合物微球的发光效率。这些研究结果将为具有特殊超分子结构和新型光学性质的苝酰亚胺功能材料的制备提供理论及实验依据，具有重要的科学意义和应用价值。