Optically Active Micellar-Cubic Liquid Crystals from Quasi-Racemic Octahedral Metallomesogens.

Macromol Rapid Commun

Department of Chemistry, College of Humanities & Sciences, Nihon University, Setagaya-ku, Tokyo, Japan.

Published: August 2025


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Article Abstract

Racemic octahedral metal complexes with Δ and Λ chirality and terminal C9 or C10 alkyl chains (M-Cn, n = 9 or 10, M = Ru or Ir) are reported as the first octahedral metallomesogens that exhibit a micellar cubic (Cub) liquid-crystal phase. The space group of the Cub phase in rac-M-Cn is , and each micelle comprises eight molecules in a J-type aggregate structure. In contrast, enantiopure Δ- and Λ-M-Cn 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 phase with a J-type aggregate structure similar to that of pure rac-M-Cn. 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.

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http://dx.doi.org/10.1002/marc.202500485DOI Listing

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