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Herein, a new family of hybrid metal halides, (DMAP)₂MBr₄(M = Cu, Zn), featuring zero‐dimensional (0D), pseudo‐layered crystal structures containing isolated molecular 4‐dimethylaminopyridinium (DMAP, C₇H₁₁N₂⁺) cations and MBr₄²⁻tetrahedral anions are reported. (DMAP)₂MBr₄show remarkable long‐term stability, with no signs of degradation after one year of ambient air exposure. The reported solution synthesis affords large crystals measuring up to 1 cm, which showed significant response to soft 8 keV X‐ray photons when implemented into X‐ray detectors. Furthermore, (DMAP)₂ZnBr₄demonstrates tunable color light emission properties, which is attributed to the organic molecular units based on our combined experimental and computational results. The measured photoluminescence quantum yield (PLQY) for (DMAP)₂ZnBr₄is 7.35 %, a remarkable enhancement of emission efficiency as compared to a weak emission from the organic precursor. The inexpensive and earth‐abundant chemical compositions and ease of preparation of the new hybrid metal halides make them promising candidates for optical and electronic applications.

Copper(I) halides are emerging as attractive alternatives to lead halide perovskites for optical and electronic applications. However, blue‐emitting all‐inorganic copper(I) halides suffer from poor stability and lack of tunability of their photoluminescence (PL) properties. Here, the preparation of silver(I) halides A₂AgX₃(A = Rb, Cs; X = Cl, Br, I) through solid‐state synthesis is reported. In contrast to the Cu(I) analogs, A₂AgX₃are broad‐band emitters sensitive to A and X site substitutions. First‐principle calculations show that defect‐bound excitons are responsible for the observed main PL peaks in Rb₂AgX₃and that self‐trapped excitons (STEs) contribute to a minor PL peak in Rb₂AgBr₃. This is in sharp contrast to Rb₂CuX₃, in which the PL is dominated by the emission by STEs. Moreover, the replacement of Cu(I) with Ag(I) in A₂AgX₃significantly improves photostability and stability in the air under ambient conditions, which enables their consideration for practical applications. Thus, luminescent inks based on A₂AgX₃are prepared and successfully used in anti‐counterfeiting applications. The excellent light emission properties, significantly improved stability, simple preparation method, and tunable light emission properties demonstrated by A₂AgX₃suggest that silver(I) halides may be attractive alternatives to toxic lead halide perovskites and unstable copper(I) halides for optical applications.