Highly Stable MOF‐Type Lead Halide Luminescent Ferroelectrics

Abstract Lead halide molecular ferroelectrics represent an important class of luminescent ferroelectrics, distinguished by their high chemical and structural tunability, excellent processability and distinctive luminescent characteristics. However, their inherent instability, prone to decomposition upon exposure to moisture and light, hinders their broader ferroelectric applications. Herein, for the first time, we present a series of isoreticular metal–organic framework (MOF)‐type lead halide luminescent ferroelectrics, demonstrating exceptional robustness under ambient conditions for at least 15 months and even when subjected to aqueous boiling conditions. Unlike conventional metal‐oxo secondary building units (SBUs) in MOFs adopting highly centrosymmetric structure with limited structural distortion, our lead halide‐based MOFs occupy structurally deformable [Pb 2 X] + (X=Cl − /Br − /I − ) SBUs that facilitate a c ‐axis‐biased displacement of Pb 2+ centers and substantially contribute to thermoinducible structural transformation. Importantly, this class of MOF‐type lead halide ferroelectrics undergo ferroelectric‐to‐paraelectric phase transitions with remarkably high Curie temperature of up to 505 K, superior to most of molecular ferroelectrics. Moreover, the covalent bonding between phosphorescent organic component and the light‐harvesting inorganic component achieves efficient spin‐orbit coupling and intersystem crossing, resulting in long‐lived afterglow emission. The compelling combination of high stability, ferroelectricity and afterglow emission exhibited by lead halide MOFs opens up many potential opportunities in energy‐conversion applications.