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Triplet exciton‐based long‐lived phosphorescence is severely limited by the thermal quenching at high temperature. Herein, we propose a novel strategy based on the energy transfer from triplet self‐trapped excitons to Mn2+ dopants in solution‐processed perovskite CsCdCl3. It is found the Mn2+ doped hexagonal phase CsCdCl3 could simultaneously exhibit high emission efficiency (81.5 %) and long afterglow duration time (150 s). Besides, the afterglow emission exhibits anti‐thermal quenching from 300 to 400 K. In‐depth charge‐carrier dynamics studies and density functional theory (DFT) calculation provide unambiguous evidence that carrier detrapping from trap states (mainly induced by Cl vacancy) to localized emission centers ([MnCl6]4−) is responsible for the afterglow emission with anti‐thermal quenching. Enlightened by the present results, we demonstrate the application of the developed materials for optical storage and logic operation applications. [ABSTRACT FROM AUTHOR]

Lead‐free halide perovskites have triggered interest in the field of optoelectronics and photocatalysis because of their low toxicity, and tunable optical and charge‐carrier properties. From an application point of view, it is desirable to develop stable multifunctional lead‐free halide perovskites. We have developed a series of Cs2PtxSn1−xCl6 perovskites (0≤x≤1) with high stability, which show switchable photoluminescence and photocatalytic functions by varying the amount of Pt4+ substitution. A Cs2PtxSn1−xCl6 solid solution with a dominant proportion of Pt4+ shows broadband photoluminescence with a lifetime on the microsecond timescale. A Cs2PtxSn1−xCl6 solid solution with a small amount of Pt4+ substitution exhibits photocatalytic hydrogen evolution activity. An optical spectroscopy study reveals that the switch between photoluminescence and photocatalysis functions is controlled by sub‐band gap states. Our finding provides a new way to develop lead‐free multifunctional halide perovskites with high stability. [ABSTRACT FROM AUTHOR]