H-Bonded metallomesogens: preparation, characterization, and mesomorphic studies of (3-hydroxypropylimino)propan-1,2-diols

Two series of new Schiff bases 2 (n=8, 12, 16) derived from (3-hydroxypropyl imino)propan-1, 2-diol with a hydroxyl group at C₁₉/C₂₀-position and their palladium complexes 1 were prepared and their mesomorphic properties investigated by DSC, POM, and XRD. The presence of both hydroxyl groups was found to be crucial in forming the liquid crystalline behavior. All compounds 2a exhibited smectic A or and C phases, in contrast, all compounds 2b formed hexagonal columnar phases. The formation of mesophases in both compounds 1-2 was probably induced by inter-molecular H-bonds. Single crystallographic data in mesogenic compound 2a (n=8) indicated that a dimeric structure with a better linear or rod-like molecular shape was formed by an inter-molecular H-bond (O4-O1′, ∼1.854 Å). Another inter-molecular H-bond (∼1.903 Å) between two dimeric structures was also observed. It crystallizes in a monoclinic space group P2(1)/c. On the other hand, all palladium complexes 1 formed enantiotropic smectic A phases. Single crystallographic data in mesogenic compound 1a (n=8) indicated that the geometry at Pd²⁺ center was coordinated as slightly twisted square planar. It crystallizes in a monoclinic space group P2(1)/n. An inter-molecular H-bond (∼1.799 Å) between neighboring molecules were observed, which might have facilitated the formation of mesophases. Variable-temperature powder XRD experiments confirmed their mesophase structures.