ABX₃-type hybrid organic–inorganic structures have recently emerged as a new class of meltable materials. Here, by the use of phenylphosphonium derivatives as A cation, we study liquid- and glass-forming behavior of a new family of hybrid structures, (RPh₃P)[Mn(dca)₃] (R = Me, Et, Ph; dca = dicyanamide). These new compounds melt at 196–237 °C (T_m) and then vitrify upon cooling to room temperature, forming glasses. In situ glass formation of this new family of materials was probed on a large scale using a variable-temperature PXRD experiment. Structure analyses of the crystalline and the glasses were carried out by solid-state nuclear magnetic resonance spectroscopy and synchrotron X-ray total scattering techniques for using the pair distribution function. The mechanical properties of the glasses produced were evaluated showing promising durability. Thermal and electrical conductivities showed low thermal conductivities (κ ∼ 0.07–0.09 W m^–1 K^–1) and moderate electrical conductivities (σ ∼ 10^–4–10^–6 S m^–1) at room temperature, suggesting that by the precise control of the A cation, we can tune meltable hybrid structures from moderate conductors to efficient thermal insulators. Our results raise attention on the practical use of this new hybrid material in applications including, e.g., photovoltaic devices to prevent light-deposited heat (owing to low κ_RT), energy harvesting thermoelectric, etc., and advance the structure–property understanding.

中文翻译：

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（RPh3P）[Mn（dca）3]： 玻璃形成杂化有机-无机材料家族


ABX₃ 型有机-无机杂化结构最近成为一类新型的可熔融材料。在这里，通过使用苯基膦衍生物作为阳离子，我们研究了一个新的杂化结构家族的液体和玻璃形成行为，（RPh₃P）[Mn（dca）₃] （R = Me， Et， Ph;dca = 双氰胺）。这些新化合物在 196–237 °C （T_m） 下熔化，然后在冷却至室温时玻璃化，形成玻璃。使用变温 PXRD 实验大规模探测了这一新材料系列的原位玻璃形成。利用对分布函数，通过固体核磁共振波谱和同步加速器 X 射线全散射技术对晶体和玻璃进行结构分析。对所生产玻璃的机械性能进行了评估，显示出良好的耐用性。热导率和电导率在室温下表现出低导热率 （κ ∼ 0.07–0.09 W m^–1 K^–1） 和中等电导率 （σ ∼ 10^–4–10^–6 S m^–1），这表明通过精确控制 A 阳离子，我们可以将可熔融的混合结构从中等导体调整为高效热绝缘体。我们的结果引起了人们对这种新型混合材料在应用中的实际应用的关注，例如，光伏器件以防止光沉积热量（由于低 κ_RT）、能量收集热电等，并促进了结构-性能的理解。