聚卟啉结构与单线态氧产率的关系

Relationship between structure and singlet oxygen yield of poly-porphyrin

摘要:

分别以5,10,15,20-四(4-羧基苯基)卟啉和4,4'-[10,20-二(4-羧基苯基)-5,15-二(2-乙炔基苯基)]卟啉与不同长度的柔性二胺为单体，通过缩合聚合制备了交联网状聚卟啉和直链聚卟啉，通过单线态氧产率的对比探究其不同结构对单线态氧产率的调控规律。结果表明，当柔性二胺中碳原子个数≤4时，交联网状聚卟啉具有优于直链聚卟啉的单线态氧产率性能，反之直链聚卟啉具有更加显著的优异性能。交联网状聚卟啉单线态氧产率随着柔性链长度的增长先上升后下降，直链聚卟啉随着柔性链长度的增长逐渐上升，且末端为同种电荷的聚卟啉具有更高的单线态氧产率, 优化后的聚卟啉其单线态氧产率可达单体的2.37倍。

Abstract:

Cross-linked or linear poly-porphyrins were prepared via polycondensation of meso-tetra (4-carboxyphenyl)porphine or 4,4'-[10,20-bis(4-ethynylphenyl)porphyrin-5,15-diyl]dibenzoic acid and diamines with various chain-lengths as monomers. The relationship between the structure of poly-porphyrin with singlet oxygen yield was explored. The results indicated that when the number of carbon atoms in the flexible diamine was less than or equal to 4, the cross-linked poly-porphyrins exhibited higher singlet oxygen yield than the linear ones. On the contrary, the linear poly-porphyrins had more remarkable performance when the number of carbon atoms in the flexible diamine was larger than 4. The singlet oxygen yield of the cross-linked poly-porphyrins first increased and then decreased with the increase of the lengths of the carbon chains, while that of linear poly-porphyrins continuously increased. Moreover, the poly-porphyrins bearing the same charges on the end groups exhibited higher singlet oxygen yield. The singlet oxygen yield of the optimized poly-porphyrin was 2.37-fold that of the monomer.