两种新型混合阳离子有机-无机杂化钙钛矿的卤素调制及物性变化，这一成果由东南大学化学化工学院叶琼研究团队经过不懈努力而取得。相关论文发表在2025年2月11日出版的《Chinese Journal of Chemistry》杂志上。

有机-无机杂化钙钛矿（OIHPs）通过取代有机阳离子和卤素来精确控制材料性能。本研究在混合阳离子体系中通过不同卤素合成了[(C₆H₁₀P)(n-BA)]Sb₂X₉ ([C₆H₁₀P]⁺ = [Me₃PCH₂CH₂CH₃]⁺, [n-BA]⁺ =正丁胺阳离子，X= I（1), Br(2)）两种oihp。卤素取代导致化合物1从稳定的无相变转变为化合物2，发生铁弹性相变（mmmF2/m）。化合物1在非中心对称的Pca2₁空间群中结晶，表现出二次谐波响应，而化合物2在纳米压痕测试中表现出弹性。卤素取代改变了Sb-X键的长度，在无机骨架中引起结构畸变，并影响有机阳离子和无机阴离子的空间构型。这些变化导致不同的结晶行为，从而导致化合物1和2的不同物理性质。这项工作有助于开发基于混合阳离子oihp中卤素调节的多功能材料。

附：英文原文

Title: Halogen Modulation and Physical Property Variation in Two Novel Mixed-Cation Organic-Inorganic Hybrid Perovskites†

Author: Xiaomei Fu, Zining Zhou, Yawen Yang, Lei He, Jie Mu, Qiong Ye

Issue&Volume: 2025-02-11

Abstract: Organic-inorganic hybrid perovskites (OIHPs) offer precise control over material properties through the substitution of organic cations and halogens. In this study, two OIHPs, [(C₆H₁₀P)(n-BA)]Sb₂X₉ ([C₆H₁₀P]⁺ = [Me₃PCH₂CH₂CH₃]⁺, [n-BA]⁺ = n-butylamine cation, X = I (1), Br (2)), were synthesized by varying halogens within a mixed-cation system. The halogen substitution induced a shift from compound 1, which remains stable without phase transitions, to compound 2, which undergoes a ferroelastic phase transition (mmmF2/m). Compound 1 crystallizes in the non-centrosymmetric Pca2₁ space group and demonstrates a second harmonic generation (SHG) response, while compound 2 displays elasticity in nanoindentation tests. Halogen substitution alters Sb—X bond lengths, inducing structural distortions in the inorganic framework and influencing the spatial configuration of organic cations and inorganic anions. These changes lead to distinct crystallization behaviors, resulting in different physical properties for compounds 1 and 2. This work contributes to the development of multifunctional materials based on halogen regulation in mixed-cation OIHPs.

DOI: 10.1002/cjoc.202401102

Source: https://onlinelibrary.wiley.com/doi/full/10.1002/cjoc.202401102