基于C–H键活化新策略设计合成卟啉类高性能近红外染料

Organic optoelectronic materials chemistry is on the rise. Dye molecules with strong absorption in near-IR(NIR) region are potentially useful but underinvestigated. To further improve the performance of optical-electronic materials, high-performance NIR dyes are highly desired. This project is going to investigate the relationship between molecular structure of porphyrins and their molar extinction coefficient(ε), based on which new NIR porphyrins are to be designed, synthesized and applied. It includes the following contents. 1) To design porphyrins with strong ε in the NIR region via calculations. 2) New strategy based on C–H direct activation, instead of traditional coupling methods, is going to be developed with features of eco-friendly, atom-economy, high efficiency and selectivity to overcome the difficulties in the synthesis of target porphyrins. 3) A diversified library of new porphyrins are to be obtained via newly developed method. Their applications in various materials are going to be discovered. 4) The structure-property-performance relationship is going to be studied. The scientific hypothesis of “desymmetrization of porphyrin increases ε” is going to be experimentally verified. . The proposer is experienced with the molecular design, synthesis and photophysical property research of porphyrins as well as device fabrication and performance optimization. If this project succeeds, the functionalization and application of porphyrins will be facilitated, the performance of devices will be improved, and the original innovation capability will be advanced in the optoelectronic area.

有机光电材料化学研究方兴未艾。在近红外区域（NIR）具有强吸收的染料分子应用前景巨大，但发展尤为不足。为进一步提升光电材料性能，针对目前有机染料分子在NIR区域吸收不够强的问题，本项目力求揭示卟啉分子结构与摩尔消光系数(ε)的相关性，并以此为基础研究新型NIR卟啉分子的设计、合成与应用。具体研究内容涵括：1) 主动设计“NIR区域ε高”的卟啉分子；2) 针对合成难点，研究卟啉C–H键活化中的科学问题，发展新型高效、高选择性、环境友好和原子经济的新方法；3) 利用新方法合成传统方法难以获得的新型特殊卟啉，开发材料应用；4) 研究构效关系，实验验证“卟啉去对称化增强ε”的科学假设。申请人在卟啉分子设计、合成、光物理性质和器件研究等方面具有一定工作积累，如获成功，将加速卟啉功能化进程，推进有机光电材料领域的发展，为提高我国有机光电领域的国际竞争力注入新的活力。

按照申请书的研究计划，本项目主要开展了五个方面的研究工作：(1)、发展了杂环芳烃嵌入的卟啉和扩展卟啉类大环分子的合成合成新策略，构筑了近红外吸收的杂芳烃稠合卟啉衍生物及咪唑环嵌入的共轭型扩展卟啉分子，研究了它们的光电性质；(2)、发展了多类简洁高效的C–H 键直接功能化反应，开发了结构多样的联芳基及稠环有机共轭骨架；(3)、基于氟硼荧的C–H键直接功能化反应发展了几类细胞荧光靶向试剂；(4)、设计合成了基于有机共轭分子的太阳能电池敏化染料，并开展了器件性能研究；(5)、设计合成了基于螺芴结构的有机发光二极管(OLED)主体材料，并开展了OLED器件性能研究。在杂环芳烃嵌入的卟啉和扩展卟啉类大环分子等联芳基及稠环有机共轭结构的构筑、电致发光器件制作及细胞成像研究方面取得了一系列创新性结果，相关研究成果在Angew. Chem. Int. Ed.、Chem. Sci.、Chem. Commun.、Org. Lett.、J. Org. Chem.等学术期刊上发表研究论文14篇，申请发明专利5项，授权4项。培养博士研究生4名，硕士研究生6名。