Discovering New Type of Lead-Free Cluster-Based Hybrid Double Perovskite Derivatives with Chiral Optical Activities and Low X-Ray Detection Limit

2D chiral hybrid perovskites have recently emerged as outstanding semiconductor materials. However, most of the reported 2D chiral perovskites have limited structural types and contain high levels of toxic lead, which severely hinders their further applications. Herein, by using a mixed-cation strategy, an unprecedented type of lead-free cluster-based 2D chiral hybrid double perovskite derivatives are successfully obtained, [(R/S-PPA)₄(IPA)₆Ag₂Bi₄I₂₄]·2H₂O ( 1-R and 1-S ), and [(R/S-PPA)₄(n-BA)₆Ag₂Bi₄I₂₄]·2H₂O ( 2-R and 2-S ) (R/S-PPA=R/S–1-phenylpropylamine; IPA=isopentylamine; n-BA=n-butylamine). Their inorganic skeletons are linked by binuclear {Bi₂I₁₀} and infinite chain {Ag₂Bi₂I₁₄}_∞, in which bismuth clusters and multiple coordination modes (e.g., tetrahedral AgI₄ and octahedral AgI₆) are introduced into the double perovskite system for the first time. This introduction induces distortion of the inorganic layer, which may facilitate the transfer of chirality from the chiral cations into achiral double perovskite skeletons. Further, circular dichroism measurements and circularly polarized light detection confirm their inherent chiral optical activities. In addition, 1-S exhibits an ultralow X-ray detection limit of 129.5 nGy s⁻¹, which is 42-fold lower than that of demands in regular medical diagnosis (5.5 µGy s⁻¹). This study provides a pathway to construct novel type of lead-free cluster-based double perovskite derivatives.