Practical synthesis of perylene-monoimide building blocks that possess features appropriate for use in porphyrin-based light-harvesting arrays

Perylene-monoimide dyes with solubilizing aryloxy substituents at the perylene perimeter and a synthetic handle on the N-aryl group are valuable building blocks for incorporation as accessory pigments in porphyrin-based light-harvesting arrays. A family of such dyes has been prepared by reaction of 1,6,9-tris(4-tert-butylphenoxy)perylene-3,4-dicarboxylic anhydride with a set of 4-iodo/ethynyl anilines (with or without 2,6-diisopropyl substituents) in the presence of Zn(OAc)2·2H2O in imidazole/mesitylene at 130°C. The workup procedures throughout the synthesis have been streamlined for scale-up purposes, minimizing chromatography. Two bis(perylene)porphyrin building blocks were prepared in a rational manner and examined in Sonogashira and Glaser polymerizations. The two isopropyl groups on the N-aryl group and the three 4-tert-butylphenoxy groups at the perylene perimeter are essential for high solubility of the bis(perylene)porphyrins and corresponding oligomers in organic solvents.