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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.202500485 | DOI Listing |
Macromol Rapid Commun
August 2025
Department of Chemistry, College of Humanities & Sciences, Nihon University, Setagaya-ku, Tokyo, Japan.
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.
View Article and Find Full Text PDFSmall
April 2025
Department of Chemistry, College of Humanities & Sciences, Nihon University, 3-25-40 Sakurajosui, Setagaya-ku, Tokyo, 156-8550, Japan.
The liquid crystalline columnar assemblies have been developed by using racemic metal complexes with Δ, Λ chirality (M-C8, M = Ru or Ir) as mesogens. A racemic M-C8 exhibits rectangular columnar (Col) and hexagonal columnar (Col) phases upon cooling from their isotropic phases, which are analyzed by the combination of grazing-incidence X-ray diffraction (GI-XRD) measurements and molecular dynamics (MD) simulation. In the Col phase, with lattice parameter a = 3.
View Article and Find Full Text PDFChem Commun (Camb)
October 2020
Department of Chemistry, School of Science, Kitasato University, 1-15-1, Kitasato, Minami-ku, Sagamihara 252-0373, Japan.
A combination of grazing-incidence X-ray diffraction and molecular dynamics simulation studies led to the visualization of the stacking structure of a helical columnar liquid crystal formed by enantiopure octahedral metallomesogens with ΔΛ chirality. The helical structure was elucidated as a hybrid of two major proposed structures.
View Article and Find Full Text PDFJ Am Chem Soc
April 2011
Department of Chemistry, University of York, Heslington, York YO10 5DD, UK.
Preparation of Ir(III) complexes using anisotropic 2,5-di(4-alkoxyphenyl)pyridine ligands leads to emissive, liquid-crystalline complexes containing bound Cl and dimethyl sulfoxide. Using analogous poly(alkoxy) ligands allows the preparation of bis(2-phenylpyridine)iridium(III) acac complexes, which are also mesomorphic. The observation of liquid crystallinity in octahedral complexes of this type is without precedent.
View Article and Find Full Text PDFJ Am Chem Soc
January 2008
Institut für Anorganische und Analystiche Chemie, Johannes-Gutenberg-Universität, Staudinger-Weg 9, D-55099 Mainz, Germany.
Three types of interplay/synergy between spin-crossover (SCO) and liquid crystalline (LC) phase transitions can be predicted: (i) systems with coupled phase transitions, where the structural changes associated to the Cr<-->LC phase transition drives the spin-state transition, (ii) systems where both transitions coexist in the same temperature region but are not coupled, and (iii) systems with uncoupled phase transitions. Here we present a new family of Fe(II) metallomesogens based on the ligand tris[3-aza-4-((5-C(n))(6-R)(2-pyridyl))but-3-enyl]amine, with C(n) = hexyloxy, dodecyloxy, hexadecyloxy, octadecyloxy, eicosyloxy, R = hydrogen or methyl (C(n)-trenH or C(n)-trenMe), which affords examples of systems of types i, ii, and iii. Self-assembly of the ligands C(n)-trenH and C(n)-trenMe with Fe(A)2 x xH2O salts have afforded a family of complexes with general formula [Fe(C(n)-trenR)](A)2 x sH2O (s > or = 0), with A = ClO4(-), F-, Cl-, Br- and I-.
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