Non‐Aqueous Lyotropic Chiral Chromonic Liquid Crystals With Solvent‐Invertible Circularly Polarized Phosphorescence

ABSTRACT This work reports non‐aqueous lyotropic chromonic liquid crystals based on chiral organometallic complexes, enabling solvent‐invertible circularly polarized luminescence from a single enantiomer of the mesogens. Cationic tridentate cyclometalated Pt(II) complexes featuring chiral hydrogen‐bonding amide groups self‐organize into chiral lyotropic chromonic mesophases at concentrations above 50 wt.% in both acetonitrile and nitromethane. At 25°C, these Pt(II) chromonic phases exhibited metal‐metal‐to‐ligand charge‐transfer (MMLCT) emissions with peak maximum at 725 nm (quantum yield 15%, lifetime 0.34 µs) in acetonitrile and 715 nm (quantum yield 18%, lifetime 0.36 µs) in nitromethane. Notably, the systems displayed opposite signs of the luminescence dissymmetry factor (g lum ) in the two solvents: typically, the R‐enantiomer of the Pt(II) mesogen showed a g lum value of −10 −1 in acetonitrile but +10 −1 in nitromethane, with the opposite behavior observed for the S‐enantiomer. Similar solvent‐dependent inversion was observed in analogous Pd(II) chromonics. Combined spectroscopic studies and molecular dynamics simulations indicate that the solvent‐modulated balance between inter‐mesogen and mesogen‐solvent interactions governs the hierarchical chirality transfer from molecular carbon‐centered chirality to supramolecular helical chirality and, ultimately, to macroscopic chromonic order.