Abstract

AbstractThe formation of an unprecedented macrocycles‐in‐a‐macrocycle (MIM) superstructure by reversible radical–radical association of a triphenylamine based monomer terminated with three dicyanomethyl radicals is presented. The reaction yield is nearly quantitative and the obtained macrocycle contains three small dimeric macrocycles according to X‐ray crystallographic analysis. The six monomer molecules are linked by nine long dynamic covalent C(sp3)−C(sp3) bonds that all adopt a gauche conformation. Such a conformation favors the formation of a MIM structure rather than a 2D network with an all‐anti conformation. Two enantiomers with left‐/ right‐handed chirality exist in the single crystals of the superstructure.

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