【摘要】 有机-无机杂化化合物因其结构可调性和多功能特性，在相变、铁电、介电及能量存储等领域展现出重要应用前景.尽管这类化合物在相变行为调控方面潜力显著，但当前基于无机阴离子调控策略的相变化合物的研究仍显不足.本研究通过无机阴离子卤素调控策略，成功构建了具有高相变温度的有机-无机杂化化合物：[Me-Q]₂ZnBr₄（1）和[Me-Q]₂ZnBr_3.8Cl_0.2（2）.单晶结构解析表明，化合物1在室温下结晶于非极性P2₁2₁2₁空间群，而化合物2在极性空间群Pna2₁中结晶.差示扫描量热仪分析证实，化合物1在299 K/287 K和309 K/301 K处、化合物2在298 K/287 K和304 K/296 K处均表现出显著的可逆相变行为.此外，Hirshfeld表面分析和二维指纹图谱表明卤素原子通过电负性差异与有机阳离子上的氢原子形成分子间作用，揭示了两种物质产生相变的原因.本研究通过无机阴离子卤素调控策略为设计高温相变有机-无机杂化化合物开辟了新方向.更多还原

【Abstract】 Organic-inorganic hybrid compounds have demonstrated significant application prospects in phase transition, ferroelectricity, dielectric properties, and energy storage due to their structural tunability and multifunctional characteristics. Despite the remarkable potential of these compounds in regulating phase transition behaviors, research on phase-transition compounds based on inorganic anion modulation strategies remains insufficient. In this study, we innovatively constructed two organic-inorganic hybrid compounds with high phase transition temperatures, [Me-Q]₂ZnBr₄（1） and [Me-Q]₂ZnBr_3.8Cl_0.2（2）,through a halogen regulation strategy targeting inorganic anions. Single-crystal structure analysis revealed that compound 1 crystallizes in the non-polar space group P2₁2₁2₁ at room temperature, while compound 2 adopts the polar space group Pna2₁. Differential scanning calorimetry（DSC） measurements confirmed distinct reversible phase transitions for compound 1 at 299 K/287 K and 309 K/301 K,and for compound 2 at 298 K/287 K and 304 K/296 K. Furthermore, Hirshfeld surface analysis and two-dimensional fingerprint plots demonstrated that halogen atoms establish intermolecular interactions with hydrogen atoms on the organic cations through electronegativity differences, elucidating the origin of phase transitions in both compounds. This work pioneers an innovative direction for designing high-temperature phase-transition organic-inorganic hybrids via inorganic anion halogen engineering.更多还原