Novel meso-substituted porphyrins:Synthesis,characterization and photocatalytic activity of their TiO2-based composites

摘要

Two series of novel meso-substituted porphyrins,namely 5,10,15,20-tetra[4-(3-phenoxy)-propox-y]phenyl porphyrin,the structural analogue 5,10,15,20-tetra[2-(3-phenoxy)-propoxy]phenyl porphyrin and their Co(II)Cu(II)and Zn(II)complexes were synthesized.The compounds were characterized using various spectroscopic techniques and their molecular structure was proposed based on density functional theory calculations.The diverse properties of the porphyrin derivatives result from the different stereochemistry of the particular substituents at the meso site on the macrocycle and are controlled also by the coordinated metal.The ~1H NMR spectrum of the free-base porphyrin showed a complicated spin-splitting.The photocatalytic activities in degradation of 4-nitrophenol were investigated using poly-crystalline TiO2 impregnated with the porphyrins and metalloporphyrins.The Cu(II)porphyrin was a more effective sensitizer than other metal containing compounds(M=Co,Zn)as well as the free-base.Photocatalytic activity was also influenced by spatial positions of the substitutions on the porphyrin molecules.