General Synthesis of Chiral Mesostructured Carbonates Using Chiral Vicinal Polyhydroxy Molecules

Although the integration of chirality with inorganic materials holds great application potential, developing general synthetic methods and achieving high optical activity remain major challenges. Inspired by biomineralization, we developed a hydrothermal method for the general synthesis of chiral carbonates using chiral vicinal polyhydroxy molecules (CVPMs). This approach enabled the formation of chiral mesostructured carbonates (CaCO₃, BaCO₃, SrCO₃, MnCO₃, CdCO₃) exhibiting pronounced circular dichroism (CD) across ultraviolet to visible regions, with the dissymmetry factor (g-factor) of Mn/CdCO₃ reaching as large as 10^-2. This is attributed to the dual role of CVPMs adsorbed on the crystal surface: they not only serve as symmetry-breaking agents but are also likely converted in situ into carbonate ions and incorporated into the lattice. This mechanism bypasses the inefficient adsorption-desorption cycles typical of conventional chiral additives. These combined features enable more efficient chirality transfer and a significantly enhanced chiroptical response. Structural analyses revealed multilevel hierarchical chirality and lattice distortions induced by CVPMs. The effectiveness of chiral induction critically depends on vicinal hydroxyl groups and controlled crystallization kinetics. These findings provide a versatile strategy for synthesizing chiral carbonates with enhanced optical properties, offering insights into chirality regulation mechanisms and expanding the toolkit for designing chiral inorganic materials.