Optically Active Micellar‐Cubic Liquid Crystals from Quasi‐Racemic Octahedral Metallomesogens

Racemic octahedral metal complexes with Δ and Λ chirality and terminal C9 or C10 alkyl chains ( M‐C n , n = 9 or 10, M = Ru or Ir) are reported as the first octahedral metallomesogens that exhibit a micellar cubic (Cub M ) liquid‐crystal phase. The space group of the Cub M phase in rac ‐ M‐C n is , and each micelle comprises eight molecules in a J‐type aggregate structure. In contrast, enantiopure Δ‐ and Λ‐ M‐C n exhibit a hexagonal‐columnar phase with helical stacking. To confirm that the Δ–Λ chiral interaction acts as a driving force for the supramolecular assembly, quasi‐racemic mixtures of Δ‐ Ru‐C9 and Λ‐ Ir‐C9 as well as Λ‐ Ru‐C9 and Δ‐ Ir‐C9 were prepared in a 1:1 molar ratio. The quasi‐racemates exhibit a Cub M phase with a J‐type aggregate structure similar to that of pure rac ‐ M‐C n . They also exhibit novel vibrational circular dichroism signals that are not observed in the enantiopure compounds, which are attributed to the close Δ and Λ packing. The obtained results suggest that mixing enantiomers in a quasi‐mirror image relationship could be a new approach for producing novel chiroptical materials.