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

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,优化后的聚卟啉单线态氧产率可达单体的2.37倍。

Cross-linked or linear poly-porphyrins were prepared via polycondensation of meso-tetra(4-carboxyphenyl)porphine or 4,4’-[10,20-bis(4-carboxyphenyl)-5,15-bis(2-ethynylphenyl)]porphyrin 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.