Chai Siqian, Xiong Jianbo, Zheng Yongshen, Shi Rongchao, Xu Jialiang
School of Chemical Engineering and Technology, Tianjin University, Yaguan Road 135, Tianjin 300350, China.
Dalton Trans. 2020 Feb 21;49(7):2218-2224. doi: 10.1039/c9dt04270a. Epub 2020 Jan 31.
Organic-inorganic hybrid compounds that undergo reversible dielectric phase transitions are a very attractive class of smart materials due to their wide applications in data storage, data communication and signal sensing. Here, a piperidine ring, CHN, was introduced into the inorganic lead halide perovskite scaffold to obtain three hybrid perovskite compounds, [CHN]PbCl (1), [CHN]PbBr (2), and [CHN]PbI (3). When compound 2 and compound 3 feature static two-dimensional (2D) and one-dimensional (1D) perovskite structures, respectively, it is striking that compound 1 shows a reversible pentahedral to octahedral transformation. It undergoes an above-room-temperature dielectric phase transition at T≅ 352 K, wherein the high dielectric constant is more than twice the low dielectric constant. Structural analysis shows that 1 undergoes a phase transition from the space group Pnma at the low temperature phase (LTP) to C2/c at the high temperature phase (HTP). The phase transition originates from the order-disorder conversion of piperidinium cations. It is interesting to note that, the Pb cations in the inorganic moieties change from five-coordinate at the LTP to six-coordinate at the HTP. The discovery of dielectric phase transition hybrid organic-inorganic lead halide perovskite materials further enhances the potential applications of high temperature responsive dielectric switchable materials.
由于在数据存储、数据通信和信号传感等领域具有广泛应用,经历可逆介电相变的有机-无机杂化化合物是一类极具吸引力的智能材料。在此,将哌啶环(CHN)引入无机卤化铅钙钛矿骨架中,以获得三种杂化钙钛矿化合物,即[CHN]PbCl(1)、[CHN]PbBr(2)和[CHN]PbI(3)。当化合物2和化合物3分别具有静态二维(2D)和一维(1D)钙钛矿结构时,引人注目的是化合物1呈现出从五面体到八面体的可逆转变。它在T≅352 K时经历高于室温的介电相变,其中高介电常数是低介电常数的两倍多。结构分析表明,1从低温相(LTP)的空间群Pnma转变为高温相(HTP)的C2/c。该相变源于哌啶鎓阳离子的有序-无序转变。有趣的是,无机部分中的Pb阳离子从LTP时的五配位变为HTP时的六配位。介电相变杂化有机-无机卤化铅钙钛矿材料的发现进一步增强了高温响应介电可切换材料的潜在应用。