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.
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Racemic Assembly of Octahedral Metallomesogens via Δ-Λ Chiral Interaction: Detection of Novel VCD Signals in Quasi-Racemate.
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February 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 PDFVisualizing the helical stacking of octahedral metallomesogens with a chiral core.
Chem 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 PDFEmissive metallomesogens based on 2-phenylpyridine complexes of iridium(III).
J 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 PDFDoes the solid-liquid crystal phase transition provoke the spin-state change in spin-crossover metallomesogens?
J 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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