含功能性构筑单元扩展卟啉的合成与性质研究

项目名称： 含功能性构筑单元扩展卟啉的合成与性质研究

项目编号： No.21501073

项目类型： 青年科学基金项目

立项/批准年度： 2016

项目学科： 数理科学和化学

项目作者： 周志宽

作者单位： 江苏科技大学

项目金额： 20万元

中文摘要： 普通四吡咯卟啉的Soret和Q带吸收均未达到近红外吸收区域（600-1000 nm）。扩展卟啉作为卟啉的衍生物具有较强的近红外吸收，它们具有作为新型高效光动力治疗光敏剂的潜力。但是，随着卟啉结构中杂环单元数量的增加，大环分子柔性增强，从而导致平面性降低，芳香性及吸收强度随之降低。本研究拟通过选取具有刚性平面结构以及包含Se、Si和Ge等特殊电子结构原子的共轭小分子作为构筑单元，合成平面性较高且π电子共轭程度增强的扩展卟啉，以期实现其吸收光谱的红移。对目标扩展卟啉分子的空间结构、芳香性及电子结构进行表征分析。利用含时密度泛函理论计算方法探讨构筑单元自身空间及电子结构对新型扩展卟啉的空间结构及芳香性的调控规律。通过对目标化合物的近红外吸收及单线态氧产生效率等应用的测试，评价其光物理性质，探索空间结构-性质之间的关系，为设计合成高效近红外光动力治疗光敏剂提供理论指导和数据支持。

中文关键词： 扩展卟啉；芳香性；近红外；光动力治疗；构效关系

英文摘要： Normal tetrapyrrole porphyrins do not show absorption in the near infrared (NIR) region (600-1000 nm). Expanded porphyrins exhibit strong absorption in NIR region compared with normal porphyrins, thus they can be used as efficient sensitizer in photodynamic therapy. However, when increase the number of heterocycles in the macrocyclic compound, their conformation become flexible, which reduce their planarity and aromaticity and thus lead to weak absorption. Herein, a series of novel expanded porphyrins are designed which embeded with functional building blocks that are highly planar and contain Se, Si and Ge atoms. The purpose is to impose planarity and enhanced aromacity to expanded porphyrins and thus to achieve near infrared absorption. The solid-state conformation, aromaticity and electronic structure will be investigated in detail. The impact of the conformational and electronic structures of building blocks on the target expanded porphyrins will be examined by using TD-DFT calculation. Near infrared absorption and singlet oxygen generation test will be carried out to estimate the photophysical performance of the target compounds and to explore the structure-property relationships, which will facilitate the rational design of expanded porphyrins with properties suitable for the application in near infrared photodynamic therapy.

英文关键词： Expanded porphyrin;Aromaticity;Near infrared;Photodynamic therapy;Relationship of structure/property