含芳香稠合构筑单元扩展卟啉的合成及其结构与光学性质的相关性研究

Porphyrinoids are widely used in the field of photodynamic therapy due to their special structure and excellent optical properties. But the drawback of absorption in the near-infrared region has always be an important issue in the design of porphyrin photosensitizer. Expansion of π-conjugated network is a common method used for modification of porphyrin structures, which lead to a reasonable red shift in the absorption spectra. Rigid structure and π-conjugated system of porphyrinoids can affect their optical properties. There are inner relationship between them. In this project, with the help of theoretical calculation, two methods, expanded and aromatic-fused manner for porphyrin modification, are chosen to regulate the absorption spectra. The fused building blocks, such as thienopyrrole, thieno-bipyrrole and carbazole, which have proper sizes and fused structures are used in the construction of expanded porphyrin. As a result, the planarity and size of π-conjugated system of macrocycles are controlled. There should be a better absorption in the given spectrum interval. Besides, the heavy atom effect which has positive effect in making redshift of absorption spectrum and in improving the efficiency in generation of reactive oxygen species, is also studied in this project. It is carried out by choosing building blocks which containing S and Se atoms for the synthesis of expanded porphyrins. The aim, exploring the relationship between structures and optical properties, will be achieved by comparing series of optical changes between different structures. Results from this project have important theoretical significance in understanding the relationship between structure of expanded porphyrin and their optical property. They can also facilitate the rational design of a new generation of porphyrinoid photosensitizer.

卟啉类化合物具有特殊的结构和光学性能，在光动力治疗领域有着广泛的应用。近红外区域的吸收缺陷是困扰卟啉类光敏剂设计的一个重要问题。卟啉π-电子共轭体系扩展，是在结构修饰的基础上，促使吸收光谱红移的一种合理设计手段。本项目拟在理论计算辅助的基础上，依据该类化合物机构刚性和π-电子体系影响其光学性质的基本原理，结合扩展卟啉和芳香稠合的设计手段，选取大小较为适宜的噻吩吡咯、噻吩并二吡咯、咔唑等芳环稠合体系作为构筑单元，合成在特定光谱区间有较理想吸收的扩展卟啉化合物；选取含有S、Se的构筑单元，利用重原子效应研究该效应对促进光谱红移效果和提高活性氧产生效率的实际效果；通过比较结构系列变化的新型目标化合物的光学性能，探索结构和光学性能之间的关系。该项目的研究成果对认识扩展卟啉化合物的结构与光学性质关系有重要的理论意义，同时可为设计合成新一代光敏剂提供理论指导和技术支持。

卟啉类化合物具有特殊的结构和光学性能，在光动力治疗领域有着广泛的应用。探索合成高活性卟啉衍生物类光敏剂尤其是在水体系中还有良好性能表现的体系具有重要的现实意义。本项目的研究工作主要集中于设计合成基于卟啉衍生物类的光动力治疗光敏剂并探索以高比表面积纳米材料为载体解决有机光敏染料在水体系中的溶解性问题，为开发更具实效性的光动力治疗体系提供有意义的参考。主要研究内容概括如下：（1）合成了具有较高光敏活性的卟烯-铱（III）金属配合物，金属铱（III）独特的光物理化学性质、大的Stokes位移和高的ISC能力结合卟烯配体在靠近近红外区域的Q带吸收强度以及卟烯本身具有的光敏活性显著的提高了化合物的光动力效果，单线态氧产生效率高达76%；（2）通过控制初始反应物浓度、水热温度、以及加热时间，利用无模板、一锅煮的简便方法合成了具有多孔分级结构的梭型二氧化钛纳米材料，进一步研究表明，该结构的比表面积相对于其它结构的纳米材料显著提高，能对有机化合物分子进行有效的吸附，在水溶液中吸附稳定性高，可以作为有机光敏剂在水体系中有效载体。项目研究期间完成了既定研究目标，所取得的研究结果为深入开展基于卟啉类光敏染料在水体系中应用的进一步研究打下了良好的基础。