Unprecedented Chiral Three-dimensional Hybrid Organic-Inorganic Perovskitoids

Chiral three-dimensional hybrid organic–inorganic perovskites (3D HOIPs) would show unique chiroptoelectronic performance due to the combination of chirality and 3D structure. However, the synthesis of 3D chiral HOIPs remains a significant challenge. Herein, we constructed a pair of unprecedented 3D chiral halide perovskitoids (R/S-BPEA)EA₆Pb₄Cl₁₅ ( 1-R/S ) (R/S-BPEA=(R/S)-1-4-Bromophenylethylammonium, EA=ethylammonium), in which the large chiral cations can be contained in the big “hollow” inorganic frameworks induced by mixing cations. Notably, 3D 1-R/S shows natural chiroptical activity, as evidenced by its significant mirror circular dichroism spectra and the ability to distinguish circularly polarized light. Moreover, based on the unique 3D structure, 1-S presents sensitive X-ray detection performance with a low detection limit of 398 nGy_air s⁻¹, which is 14 times lower than the regular medical diagnosis of 5.5 μGy_air s⁻¹. In this work, 3D chiral halide perovskitoids provide a new route to develop chiral material in spintronics and optoelectronics.