Thio‐Tetracosulene: A Highly Twisted Molecular Plectoneme

Abstract We report the synthesis and characterization of thio‐tetracosulene 3 , a highly twisted chiral macrocycle constructed via sulfur fluorine annulative substitution from a cyclometaphenylene derivative. It is the first macrocyclic aromatic compound with a plectonemic configuration, and the structure is unambiguously confirmed by single crystal X‐ray diffraction study. The two enantiomers of 3 can be resolved to investigate their chiroptical properties. In contrast to the known topological knot‐, or Möbius‐type macrocycles which induce chirality by specific connection patterns, the asymmetric structure of 3 is formed and maintained by the tendency of a ring in distress to reduce unfavorable strains.