Harata-Kodaka's rule predicting the induced chirality of the guest molecules by cyclodextrins has been discovered in the 1970-1990s, yet its ability to control the supramolecular handedness of self-assembled structures has not been sufficiently recognized. Here we show that in a coordinating self-assembly system that is able to form racemic cone shells symmetry breaking occurs if the ligand is prethreaded into α-cyclodextrin prior to metal ion addition, and the handedness of cone shells can be rationally manipulated by creating the two scenarios of the Harata-Kadaka rule through controlling the host-guest dynamics. Since the coordination complexes have strong self-assembling ability, the coordinating ligand would dethread from the cavity of α-cyclodextrin but leaving the induced chirality to the coordinating self-assembly, thus catalyzing symmetry breaking. This work reveals that the dynamic factors such as concentration and molar ratio may play important roles in symmetry breaking at the supramolecular level. The current strategy provides a promising method for the symmetry breaking and manipulation of the handedness of self-assembled materials formed by achiral molecules.
Keywords: Harata−Kodaka’s rule; catassembly; host−guest dynamics; symmetry breaking; α-cyclodextrin.