Abstract
A class of triple-stranded helicates based on six-coordinate silicon centres has been constructed through self-assembly of achiral catechol ligands, as confirmed by single-crystal X-ray diffraction. These architectures demonstrate stability across physiological environments at pH = 3-12. Ligand rigidity dictates chiral configurations: rigid scaffolds form ΛΛ/ΔΔ racemic helicates, while flexible linkers enable dynamic equilibration with ΛΔ mesostates, observable by NMR. Host-guest interactions drive mesocate to helicate conversion, imparting cage-like guest recognition behavior. The helicates combine the biocompatibility of silicon with ligand-controlled chirality switching, offering potential for biomimetic applications.