A Fullerene‐Substituted Pillar[5]arene for the Construction of a Photoactive Rotaxane

Abstract

Transformation of a methylene group of the pillar[5]arene scaffold into a ketone has been achieved by treatment with N‐bromosuccinimide followed by hydrolysis of the bromide intermediate and oxidation of the resulting secondary benzylic alcohol with BaMnO4. Condensation of the resulting macrocycle including a ketone function with p‐toluenesulfonyl hydrazide followed by reaction of the corresponding tosylhydrazone with C60 under modified Bamford–Stevens conditions gave a fulleropillar[5]arene derivative. This building block has been used to prepare a rotaxane. The resulting molecule combining the fullerene‐functionalized macrocycle with an axle bearing a porphyrin stopper is a photoactive molecular device in which the porphyrin emission is efficiently quenched by the fullerene moiety.