单元刚性方格的逆向合成分析及其快捷、高效合成

Comparing with macrocycles, grid structure exhibits good inter-connecting characteristic and provides a unique molecular module for materials and biological science. The project is committed to designing a novel rigid grid units. Under the guidance of retrosynthetic analysis, the total synthesis of grid units are carry out using fluorenes as a starting material. This project focuses on: 1. Friedel-Crafts and other coupling reaction such as Suzuki and C-H activation as common strategies to synthesize grids; 2. Many effects associated with cyclization are considered involving monomer skeleton shape effects including I-shape, L-shape and U-shape synthons, substitution effects and external environment conditions. Final, we build optimized synthetic routes for fluorene-based nano-sized monomer grid with artistic shape involving trapezoid, windmill and well-shape, which shows great development potential for nanotechnology, optoelectronics and other fields.

与大环结构比较，方格结构具有较好的互联特征，将为材料与生命科学相关领域的应用提供特有的分子模块。本项目以芴或类芴结构作为构建模块，设计新颖的单元刚性方格结构，在逆合成分析指导下，开展其全合成构筑。本项目主要研究：1）以傅克反应为基础，系统拓展多种快捷、高效原型反应，尝试过渡金属催化的C-C偶联反应和C-H功能化反应等；2）研究单体骨架形状效应（包括I形单体、L形单体和U形单体等）、取代基效应以及外部条件对反应的影响。最终建立芴基单元格子的最佳合成路线，合成出一系列纳米尺度的梯形、风车以及井字单元方格，为纳米与光电等领域提供功能结构单元。

本项目围绕芴以及类芴格芳烃的设计、合成及其光电性质研究展开工作，在实施过程中，设计一系列纳米尺度的梯形、风车、缺角形、3D以及井字形格芳烃；发现L形单体经由二聚傅克环化能够高效的合成梯形、风车和缺角形格芳烃。借助超分子吸引力与超亲电体的电荷排斥，可以有效调控梯形和缺角形格芳烃的立构选择性。明确二聚芴叔醇的异构体对3D格芳烃异构体的立构选择性没有影响，仅影响其产率。相比于未环化的单体，这些格芳烃表现出较好的热稳定性、电化学稳定性、光谱稳定性，这为纳米和光电等领域提供了新的功能结构单元。相关成果已经发表包括Nature Communications, Journal of Organic Chemistry, Organic & Biomolecular Chemistry, European Journal of Organic Chemistry等SCI期刊论文11篇，获授权专利3项和申请发明专利10项，培养硕士毕业生3名。