Strain-Driven Solid–Solid Crystal Conversion in Chiral Hybrid Pseudo-Perovskites with Paramagnetic-to-Ferromagnetic Transition,Journal of the American Chemical Society

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Strain-Driven Solid–Solid Crystal Conversion in Chiral Hybrid Pseudo-Perovskites with Paramagnetic-to-Ferromagnetic Transition
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-02-02 , DOI: 10.1021/jacs.2c12525
Haining Zheng _{1,

2} , Rongrong Zhang _{1,

2} , Xiao Wu ₂ , Qihan Zhang ₃ , Zhenyue Wu ₂ , Walter P D Wong ₂ , Jingsheng Chen ₃ , Qing-Hua Xu ₂ , Kian Ping Loh _{1,

2}

Affiliation

Hybrid organic–inorganic perovskites (HOIPs) are promising stimuli-responsive materials (SPMs) owing to their molecular softness and tailorable structural dimensionality. The design of mechanically responsive HOIPs requires an in-depth understanding of how lattice strain induces intermolecular rearrangement that impacts physical properties. While chirality transfer from an organic cation to an inorganic lattice is known to influence chiral-optical properties, its effect on strain-induced phase conversion has not been explored. As opposed to achiral or racemic organic cations, chiral organic cations can potentially afford a new dimension in strain-responsive structural change. Herein, we demonstrate that mechanical strain induces a solid phase crystal conversion in chiral halide pseudo-perovskite single crystals (R/S)-(FE)₂CuCl₄ (FE = (4-Fluorophenyl)ethylamine) from a 0D isolated CuCl₄ tetrahedral to 1D corner-sharing CuFCl₅ octahedral framework via the incorporation of Cu···F interaction and N–H···F hydrogen bonding. This strain-induced crystal-to-crystal conversion involves the connection of neighboring 0D CuCl₄ tetrahedra via Cu²⁺–Cl^––Cu²⁺ linkages as well as the incorporation of a F-terminated organic cation as one of the X atoms in BX₆ octahedra, leading to a reduced band gap and paramagnetic-to-ferromagnetic conversion. Control experiments using nonchiral or racemic perovskite analogs show the absence of such solid phase conversion. To demonstrate pressure-sensitive properties, the 0D phase is dispersed in water-soluble poly(vinyl alcohol) (PVA) polymer, which can be applied to a large-scale pressure-induced array display on fibrous Spandex substrates via a screen-printing method.

中文翻译：

具有顺磁到铁磁转变的手性杂化拟钙钛矿中的应变驱动固-固晶体转换

杂化有机-无机钙钛矿 (HOIP) 是一种很有前途的刺激响应材料 (SPM)，因为它们具有分子柔软性和可定制的结构维度。机械响应 HOIP 的设计需要深入了解晶格应变如何引起影响物理性质的分子间重排。虽然已知从有机阳离子到无机晶格的手性转移会影响手性光学性质，但尚未探索其对应变诱导的相转换的影响。与非手性或外消旋有机阳离子相反，手性有机阳离子可能为应变响应结构变化提供新的维度。在这里，我们证明了机械应变在手性卤化物伪中引起固相晶体转化-钙钛矿单晶 ( R / S )-(FE) ₂ CuCl ₄ (FE = (4-Fluorophenyl)ethylamine) 从 0D 孤立的 CuCl ₄四面体到 1D 角共享 CuFCl ₅八面体骨架，通过掺入 Cu··· F相互作用和N-H···F氢键。这种应变诱导的晶体到晶体的转换涉及通过 Cu ²⁺ –Cl ^– –Cu ^{2+键连接相邻的 0D CuCl}₄四面体，以及引入 F 端有机阳离子作为 X 原子之一BX ₆八面体，导致带隙减小和顺磁到铁磁的转换。使用非手性或外消旋钙钛矿类似物的对照实验表明不存在这种固相转化。为了展示压敏特性，0D 相分散在水溶性聚（乙烯醇）(PVA) 聚合物中，可通过丝网印刷方法将其应用于纤维氨纶基板上的大规模压力诱导阵列显示器.

更新日期：2023-02-02

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