One-Dimensional Cadmium Thiocyanate Perovskite Ferroelastics Tuned by Halogen Substitution,Chemistry of Materials

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One-Dimensional Cadmium Thiocyanate Perovskite Ferroelastics Tuned by Halogen Substitution
Chemistry of Materials ( IF 7.2 ) Pub Date : 2019-12-10 , DOI: 10.1021/acs.chemmater.9b04232
Lei He ₁ , Lin Zhou ₁ , Ping-Ping Shi ₁ , Qiong Ye ₁ , Da-Wei Fu ₁

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Organic–inorganic hybrid molecular ferroelastics have gained widespread attention as a promising candidate for data storage, sensor, and mechanical switch applications. However, it remains a great challenge to construct new molecular ferroelastic materials. Based on the “quasi-spherical theory”, we designed and synthesized a new quasi-spherical cation [DMIE]⁺ ([DMIE]⁺ is dimethyl-isopropyl-ethyl-ammonium cation) to expect ferroelastic materials. Unfortunately, [DMIE][Cd(SCN)₃] (1) undergoes a structural phase transition from the space group P6₃ to P6₃/mmc, which is not among the 94 species of ferroelastic phase transitions as suggested by Aizu. Herein, by introducing electronegative halogen (F, Cl, or Br) atoms to the [DMIE]⁺ cation, the symmetry groups of the corresponding cadmium thiocyanate perovskites get efficiently lowered to orthorhombic Pbca to induce ferroelastic phase transitions with an Aizu notation of 6/mmmFmmm. The spontaneous strain value reduces from 0.0778 in a fluorinated product to 0.0428 in a brominated product. Accompanied by the introduction of halogen groups from F to Br, the phase transition temperature increases from 248.6 to 367.8 K. This work demonstrates that the strategy of combining a quasi-spherical molecule with specific electronegative groups provides an efficient way to offer molecular ferroelastic materials.

中文翻译：

通过卤素取代调整一维硫氰酸镉钙钛矿铁弹性体

作为数据存储，传感器和机械开关应用的有希望的候选者，有机-无机杂化分子铁弹性体已获得广泛关注。然而，构建新的分子铁弹性材料仍然是一个巨大的挑战。基于“准球形理论”，我们设计并合成了一种新的准球形阳离子[DMIE] ⁺（[DMIE] ⁺是二甲基-异丙基-乙基-铵阳离子），有望获得铁弹性材料。不幸的是，[DMIE] [Cd（SCN）₃ ]（1）经历了从空间群P 6 ₃到P 6 ₃ / mmc的结构相变。，这不是Aizu提出的94种铁弹性相变中的一种。在此，通过将负电性卤素（F，Cl或Br）原子引入[DMIE] ⁺阳离子，相应的硫氰酸镉钙钛矿的对称基团有效地降低为正交晶的Pbca，从而引起铁弹性相变，Aizu表示为6 / mmmFmmm。自发应变值从氟化产品中的0.0778降低到溴化产品中的0.0428。伴随着从F到Br引入卤素基团，相变温度从248.6升高到367.8K。这项工作表明，将准球形分子与特定负电性基团结合的策略提供了一种提供分子铁弹性材料的有效方法。

更新日期：2019-12-11

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