β-Perfluoroalkylated meso-Aryl-Substituted Subporphyrins: Synthesis and Properties

Abstract

A convenient and effective synthesis of various novel β-perfluoroalkylated subporphyrins has been developed. β-Trifluoromethylated subporphyrins were efficiently synthesized by the reaction of brominated subporphyrins with FSO₂CF₂CO₂Me/CuI [with or without Pd(dba)₂]. Potentially valuable β-perfluoroalkylated, β-monotetrafluorobenzo, and β-monotrifluorobenzo subporphyrins were successfully obtained by a modified sulfinatodehalogenation reaction. Photophysical and electrochemical studies on several typical perfluoroalkylated subporphyrins demonstrated that β-hexakistrifluoromethylated subporphyrins show an obviously red-shifted UV/Vis absorption band that arises from macrocycle nonplanar distortion induced by trifluoromethyl groups, but this distortion is not so severe as that of the corresponding β-octakis(trifluoromethyl)-meso-tetraphenylporphyrin. This was supported by their redox potential data. In addition, β-monotrifluorobenzo subporphyrin exhibits a special fluorescence spectrum of vibronic structure.

Key words

subporphyrin - palladium - perfluoroalkyl - trifluoromethylation - sulfinatodehalogenation

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