Hybrid Metal Halides with Multiple Photoluminescence Centers

Very little is known about the realm of solid‐state metal halide compounds comprising two or more halometalate anions. Such compounds would be of great interest if their optical and electronic properties could be rationally designed. Herein, we report a new example of metal halide cluster‐assembled compound (C₉NH₂₀)₉[Pb₃Br₁₁](MnBr₄)₂, featuring distinctly different anionic polyhedra, namely, a rare lead halide cluster [Pb₃Br₁₁]^5? and [MnBr₄]^2?. In accordance with its multinary zero‐dimensional (0D) structure, this compound is found to contain two distinct emission centers, 565 nm and 528 nm, resulting from the formation of self‐trapped excitons and ⁴T₁‐⁶A₁ transition of Mn²⁺ ions, respectively. Based on the high durability of (C₉NH₂₀)₉[Pb₃Br₁₁](MnBr₄)₂ upon light and heat, as well as high photoluminescence quantum yield (PLQY) of 49.8 % under 450 nm blue light excitation, white light‐emitting diodes (WLEDs) are fabricated, showcasing its potential in backlight application.