Enantiomeric Control of Intrinsically Chiral Nanocrystals

The chiral aspect of inorganic crystals that crystallize in chiral space groups has been largely ignored until recently, partly due to difficulties in characterizing the chiroptical properties of bulk crystals, and also due to the difficulty in separating (sub)micrometer‐scale chiral crystal enantiomers. In recent years, the colloidal synthesis of intrinsically chiral nanocrystals (NCs) of several chiral inorganic compounds with significant enantiomeric excess has been demonstrated. This is achieved through the use of chiral molecular ligands, which bind to the atomic/ionic components of the crystals, preferentially forming one crystal enantiomorph. Here, recent progress on several aspects of these NCs is described, including the connection between ligand structure and its ability to direct NC handedness, chiral amplification in the synthesis leading to enantiopure NC samples, spontaneous symmetry breaking, the formation of NCs with chiral shapes, the connection between lattice and shape chirality and mixed contributions of atomic‐scale and shape chirality to the chiroptical properties. Chiral nanocrystals can be prepared with high enantioselectivity by utilizing chiral biomolecules. The several chiral nanocrystal systems that have been studied so far are reviewed with insights on the role of the chiral molecules and the possible mechanisms that may lead to chiral shape formation. The imprinting of the chiral shape to achiral functional materials is discussed.