Abstract

AbstractA “rim‐differentiated” pillar[6]arene (RD‐P[6]) was obtained successfully, with the assistance of a dimeric silver trifluoroacetate template, among eight different constitutional isomers in a direct and regioselective manner. The solid‐state conformation of this macrocycle could switch from the 1,3,5‐alternate to a truly rim‐differentiated one upon guest inclusion. This highly symmetric RD‐P[6] not only hosts metal‐containing molecules inside its cavity, but also can form a pillar[6]arene‐C60 adduct through co‐crystallization on account of donor‐acceptor interactions. The development of synthetic strategies to desymmetrize pillararenes offers new opportunities for engineering complex molecular architectures and organic electronic materials.

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