具有铁电性和铁弹性共存的轴手性 BINOL 多铁性晶体,Journal of the American Chemical Society

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具有铁电性和铁弹性共存的轴手性 BINOL 多铁性晶体
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2022-10-12 , DOI: 10.1021/jacs.2c08667
Yu-Ling Zeng ₁ , Yong Ai ₁ , Shu-Yu Tang ₁ , Xian-Jiang Song ₁ , Xiao-Gang Chen ₁ , Yuan-Yuan Tang ₁ , Zhi-Xu Zhang ₂ , Yu-Meng You ₂ , Ren-Gen Xiong ₃ , Han-Yue Zhang ₃

Affiliation

从天然氨基酸到粒子物理学，手性无处不在。最近已证明引入点手性是构建分子铁电体的有效策略。然而，与点手性相反，到目前为止，轴向手性很少用于设计铁电体。在这里，基于光学活性 1,1'-bi-2-naphthol (BINOL)，它已被广泛用作不对称催化、手性识别和光学中的多功能手性试剂，我们成功设计了一对轴向手性 BINOL多铁性， ( R )-BINOL–DIPASi 和 ( S)-BINOL-DIPASi。它们分别在 362 和 363 K 的高温下经历 2F1 型全铁电/铁弹性相变。压电力显微镜和极化电压磁滞回线展示了它们的铁电畴和畴切换，偏振光显微镜可视化了条形铁弹性畴的演变。轴向手性 BINOL 结构单元促进了极性结构和铁电性的产生，而有机硅组分增加了旋转能垒，从而提高了相变温度。这项工作展示了第一个轴向手性高温多铁性晶体，为通过引入轴向手性设计分子多铁性提供了一条有效的途径。

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Axial-Chiral BINOL Multiferroic Crystals with Coexistence of Ferroelectricity and Ferroelasticity

Chirality exists everywhere from natural amino acids to particle physics. The introduction of point chirality has recently been shown to be an efficient strategy for the construction of molecular ferroelectrics. In contrast to point chirality, however, axial chirality is rarely used to design ferroelectrics so far. Here, based on optically active 1,1′-bi-2-naphthol (BINOL), which has been applied extensively as a versatile chiral reagent in asymmetric catalysis, chiral recognition, and optics, we successfully design a pair of axial-chiral BINOL multiferroics, (R)-BINOL–DIPASi and (S)-BINOL–DIPASi. They experience a 2F1-type full ferroelectric/ferroelastic phase transition at a high temperature of 362 and 363 K, respectively. Piezoelectric force microscopy and polarization–voltage hysteresis loops demonstrate their ferroelectric domains and domain switching, and polarized light microscopy visualizes the evolution of stripe-shaped ferroelastic domains. The axial-chiral BINOL building block promotes the generation of the polar structure and ferroelectricity, and the organosilicon component increases the rotational energy barrier and thus the phase transition temperature. This work presents the first axial-chiral high-temperature multiferroic crystals, offering an efficient path for designing molecular multiferroics through the introduction of axial chirality.

更新日期：2022-10-12

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