新型杂环丁二烯卟啉及其金属配合物的合成与性能研究

丁二烯卟啉是一种缺失了一个氮原子四元卟啉，它具有良好的平面性和稳定性。由于丁二烯卟啉环内空腔较大，它具有更强的金属配位能力和多样的配位方式，且环内丁二烯可通过灵活翻转来调控卟啉在Hückel和Möbius构型之间转换。由于合成方法的限制，使其结构局限于全吡咯丁二烯卟啉的研究。本项目拟通过分子内的偶联反应设计合成一系列新型的含有呋喃环、噻吩环、硒吩环、碲吩环等杂环的丁二烯卟啉衍生物及其金属配合物，结合理论计算，详细研究杂原子的引入和meso位的电子效应对丁二烯卟啉的光谱影响及变化规律；研究杂环丁二烯卟啉与金属的配位能力和配位方式；研究光照对杂环丁二烯卟啉金属配合物的双键的影响及产生单线态氧的能力。本项目为新型丁二烯卟啉的合成及其应用研究提供必要的实验支持和理论基础。

Compared with the ordinary porphyrin, butadieneporphyrin devoid of one nitrogen atom in a pyrrole ring, it has good planarity and stability. Due to the larger cavity of the butadieneporphyrin ring, it has stronger metal coordination ability and various coordination modes, and butadiene in the ring can be used to control the conversion of porphyrins between the Hückel and Möbius configurations. Due to the limitation of the synthesis method, the structural study is limited to the whole pyrrole-butadieneporphyrin. This project intends to design and synthesize a series of novel butadieneporphyrin derivatives and their metal complexes containing heterocyclic rings such as furan ring, thiophene ring, selenophene ring, tellurophene ring, in order to investigate the structure of butadieneporphyrin and its complex nature. The theoretical calculations and experimental tests were combined to study in detail: the effects of heteroatom introduction and electron effect of meso substituent on the spectra of butadiene porphyrin were investigated in detail; the coordination ability and coordination mode of heterocyclic porphyrin with metal were studied; the influence of light on the double bond of heterocyclic porphyrin metal complex and the ability to generate singlet oxygen. This project provides the necessary experimental support and theoretical basis for the synthesis of novel butadiene porphyrin and its application.