Chiral Hierarchical Architecture Induced by Confinement-Assisted Living Supramolecular Polymerization of Simple Achiral Molecules.

Chiral supramolecular assembly (CSA) based on achiral molecules has provided important clues to understand the origin of biological chirality. However, a simple achiral monomer faces the challenge of chiral stacking with the absence of a chiral resource. The difficulty is that simple achiral monomer lacks steric repulsion to provide asymmetry during hierarchical assembly, which is a prerequisite for chiral stacking with an angle. Moreover, during chiral stacking of achiral molecules or units, the right-handed and left-handed chiral supramolecular isomers (CSIs) are equally formed due to the mirror-imaged conformation, which leads to chirality silence. Here, with the benefit of two-dimensional confinement space of layered double hydroxide (LDH), simple achiral molecules can be arranged to staggered bilayer arrays by imprinting the topological structure of LDH. Once LDH is removed, these staggered arrays can form asymmetric living seeds, which can further elongate to living units with the advantage of living supramolecular polymerization (LSP) by following off-pathway. Due to the asymmetry of living units, the possible chiral stacking outcomes, CSIs, are not mirror-imaged. With the increase of the molecular number in living units, the energy difference between CSIs can be amplified by self-replication of LSP, leading to handedness preference. Thus, the detectable CSA is mainly derived from the CSI with energetically favored hierarchical structure. Thus, our strategy breaks the stereotype that the complex molecular structure and symmetry breaking mechanism are necessary for the formation of detectable CSA by achiral molecules.