Bottom‐Up Design of Chiral Hybrid Metal Halides via Exogenous Chiral‐Center Graft Strategy

2 reaction between homochiral epoxy chloropropane and achiral amines, a series of CHMs is successfully bottom-up designed. All the CHMs obtained from the strategy crystalize in the chiral space group and exhibit significant chiral characters including chiroptical activity and secondary harmonic generation. Additionally, the introduction of the exogenous chiral centers promotes the materials exhibit inherent chiral semiconductor features, which enables them to own the capability to intertangle with light with different states of helicity, provoking them potential in the application of circularly polarized light emission and detection. This work provides a new routine to design and synthesize CHMs conveniently and robustly, which may boost further investigation of chiral sciences.