AbstractScintillators, essential for applications in nuclear medicine, radiation detection, and industrial inspection, convert high‐energy radiation into visible light. Manganese (Mn)‐based inorganic–organic hybrid materials are distinguished by their thermal stability, mechanical strength, and flexibility. However, the effects of temperature on Mn(II)‐based hybrid scintillators have not been clearly analyzed, making the elucidation of their temperature‐dependent luminescence mechanisms particularly important. A notable advancement is the synthesis of Mn‐1 nanocrystals (NCs) using methyltriphenylphosphonium chloride (mtppCl) and MnCl₂. These NCs exhibit distinctive temperature‐dependent photoluminescence luminescence: the intensity decreases from 77 to 150 K but paradoxically increases at higher temperatures due to anomalous thermal exciton behavior in the [MnCl₄]2⁻ tetrahedra. Besides, Mn‐1 NCs achieve a detection limit of 1.01 µGyair/s, surpassing medical diagnostic standards and outperforming commercial scintillators such as Bi₄Ge₃O₁₂ (BGO). Additionally, they show exceptional stability under continuous irradiation and can be incorporated into a flexible scintillating film with a resolution of 11.3 lp/mm at an MTF of 0.2. The current study has further refined the luminescence mechanism of Mn(II)‐based materials and optimizes their properties for a wider range of applications.
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