A strategy to reversibly switch the parallel/antiparallel helical conformation of aromatic double helices through the formation/breakage of a disulfide bond is presented. Single‐crystal X‐ray structures, NMR, and circular dichroism spectroscopy demonstrate that the double helices with terminal thiol groups favor an antiparallel helical arrangement both in the solid state and in solution, while the P/M bias of helicity induced by chiral segments from another extremity of the sequence is weak in this structural motif. The antiparallel helices can be rearranged to parallel helices through the disulfide connection of the sequences. This change enhances the bias of helical handedness and results in absolute chirality control of the double helices. The handedness‐mediated process can be governed by the oxidation‐reduction cycle, thereby switching the structural arrangement and the enhancement of chiral bias. In addition, we find that the sequences can dimerize into an intermolecular double helix with the disulfide connection. And the helical handedness is also fully controlled due to the head‐to‐head structural motif.

A series of quinoline–triazole oligomers self-assembled into quadruple helical structures is presented.

Invited for the cover of this issue is the group of Michel Rickhaus at the University of Zurich. The image depicts the “unearthing” of the highly contorted azatriseptane, a carbon framework consisting of three fused seven‐membered rings surrounding a central nitrogen. Read the full text of the article at 10.1002/chem.202203954.

Unearthing azatriseptane: Explore the properties and potential of a newly synthesized, highly strained carbon framework with a nitrogen core, containing three fused heptagon rings. This heterocycle could serve as an encouraging platform from which to explore the supramolecular behavior of these contorted hydrogen‐bonding systems or to obtain negatively curved nanographenes. More information can be found in the Research Article by M. Rickhaus and co‐workers (DOI: 10.1002/chem.202203954).