Chiral zero-dimensional (0D) hybrid metal halides, merging chirality with exceptional emission properties, are highly promising for circularly polarized luminescence (CPL). For CPL applications, it is difficult to simultaneously achieve large dissymmetry factor (glum) and photoluminescence quantum yield (PLQY). Herein, we propose a chemical design strategy to systematically control the glum and PLQY. We take achiral or chiral organic cations, to partially substitute the original A-site in A3SbCl6 (A = (R/S)-morpholin-2-ylmethanol, R/S-MOR), to form ordered chiral-achiral halides (A)2(B)SbCl6 (B = ethylammonium, iso-propylammonium, 2-chloroethylammonium, n-propylammonium, n-butylammonium), and ordered mixed chiral-chiral halides (A)2(C)SbCl6 (C = (R/S)-1-amino-2-propanol), respectively. The introduction of different natures of cations not only systematically alters the PLQY (up to 86.0%) by increasing the Sb⋯Sb distances and [SbCl6]3− octahedral distortion, but also significantly amplifies the chirality with enhanced glum. Among them, the mixed chiral-chiral material achieves the largest glum value (∼9 × 10−3) with a high PLQY of 71.6%. The added dimension of a different chiral source reinforces the chirality and suppresses the inorganic octahedra vibration via hydrogen bonding interactions between the hydroxyl group and [SbCl6]3− octahedra. This work showcases an effective strategy to enhance the chiroptic properties and unlocks a large variety of new functional hybrid halides with ordered chiral/achiral cation combinations.
