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 [Pb2X]+ (X=Cl−/Br−/I−) SBUs that facilitate a c‐axis‐biased displacement of Pb2+ 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.

中文翻译：

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高度稳定的 MOF 型卤化铅发光铁电体


卤化铅分子铁电体是一类重要的发光铁电体，以其高化学和结构可调性、优异的加工性能和独特的发光特性而著称。然而，它们固有的不稳定性，暴露在潮湿和光线下容易分解，阻碍了它们更广泛的铁电应用。在此，我们首次提出了一系列等网状金属有机骨架（MOF）型卤化铅发光铁电体，在环境条件下至少 15 个月甚至在水沸腾条件下表现出卓越的鲁棒性。与 MOF 中采用高度中心对称结构且结构变形有限的传统金属氧二次结构单元 (SBU) 不同，我们的卤化铅基 MOF 占据结构可变形的 [Pb2X]+ (X=Cl−/Br−/I−) SBU，从而促进Pb2+ 中心的 c 轴偏向位移，对热诱导结构转变有很大贡献。重要的是，这类 MOF 型卤化铅铁电体经历铁电到顺电相变，居里温度高达 505 K，优于大多数分子铁电体。此外，磷光有机成分和光捕获无机成分之间的共价键实现了有效的自旋轨道耦合和系间窜越，从而产生长寿命的余辉发射。卤化铅 MOF 展现出的高稳定性、铁电性和余辉发射的引人注目的组合，为能量转换应用开辟了许多潜在的机会。