Novel 5-benzazolyl-10,15,20-triphenylporphyrins and β,meso-benzoxazolyl-bridged porphyrin dyads: Synthesis, characterization and photophysical properties

Novel 5-benzazolyl-10,15,20-triphenylporphyrins and β,meso-benzoxazole-linked diporphyrins were synthesized through La(OTf)3 catalyzed reaction of newly prepared 5-(3,4-diaminophenyl)-10,15,20-triphenylporphyrin or 5-(3-amino-4-hydroxyphenyl)-10,15,20-triphenylporphyrin with aromatic aldehydes in 1,2-dichlorobenzene. On metalation with zinc acetate, freebase β,meso-benzoxazole-linked diporphyrin was successfully converted to the Zn–Zn diporphyrin complex in good yield. The synthesized porphyrin analogues were characterized using electronic absorption, IR and 1H NMR spectroscopy in addition to mass and elemental analyses. The fluorescence studies of 5-benzazolyl-10,15,20-triphenylporphyrins showed efficient intramolecular energy transfer from the pyrene and fluorene subunits to the porphyrin core. In addition, the fluorescence quenching observed in β,meso-benzoxazolyl-bridged porphyrin dyads was attributed to the possible nonplanarity of a component of the diporphyrins. The freebase–Ni diporphyrin complex underwent strong emission quenching in comparison to that of freebase diporphyrin and dizinc diporphyrin analogues.

Graphical abstractFigure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Two new porphyrin precursors have been synthesized and characterized. ► An efficient protocol for 5-benzazolyl-10,15,20-triphenylporphyrins through La(OTf)3 catalyzed reaction. ► Extension of methodology to obtain β,meso-linked porphyrin dyads with benzoxazole spacer. ► Photophysical investigation shows an efficient intramolecular energy transfer in porphyrin dyads.