Musozoda Muhammadiqboli, Bishuk Andrew L, Britton Blake J, Scheuren Marija, Laber Charles H, Baker Gary A, Baker Matthew S, Zeller Matthias, Paull Daniel H, Hillesheim Patrick C, Mirjafari Arsalan
Department of Chemistry, State University of New York at Oswego, Oswego, New York 13126, United States.
Department of Chemistry and Physics, Ave Maria University, Ave Maria, Florida 34142, United States.
ACS Appl Eng Mater. 2025 May 5;3(5):1468-1482. doi: 10.1021/acsaenm.5c00221. eCollection 2025 May 23.
We have developed a class of organophosphorus ionic materials featuring tetraarylphosphonium cations with extended π-conjugated systems via a facile and modular approach. These mesothermal ionic liquids demonstrate exceptional thermal stability, maintaining their structural integrity when heated at 300 °C for 96 h under aerobic conditions without decomposition. Their negligible volatility and strategic exclusion of aliphatic C-(sp)-H bonds from our molecular architecture yields materials with outstanding resistance to thermo-oxidative degradation. Our rigorous investigation using comprehensive single-crystal X-ray diffraction and thermodynamic studies validates the design principles while providing detailed insights into the structure-property relationships governing their thermal stability, melting behavior, and photophysical properties. Our studies reveal a systematic correlation between the nature of the cations and the resulting phase transitions. Additionally, detailed photophysical characterization demonstrates that select derivatives exhibit strong fluorescence with quantum yields up to 42%, suggesting potential applications in optoelectronic devices. These thermally robust organic-ion materials with tunable properties have potential applications ranging from thermally demanding environments (thermoresponsive materials, advanced nuclear reactor coolants, and thermal energy storage) to optoelectronic devices that capitalize on their unique photoluminescent characters.
我们通过一种简便且模块化的方法，开发了一类具有扩展π共轭体系的四芳基鏻阳离子的有机磷离子材料。这些介热离子液体表现出卓越的热稳定性，在有氧条件下于300°C加热96小时仍能保持其结构完整性而不分解。它们可忽略不计的挥发性以及我们分子结构中对脂肪族C-(sp)-H键的策略性排除，产生了具有出色抗热氧化降解性能的材料。我们使用全面的单晶X射线衍射和热力学研究进行的严格调查验证了设计原则，同时深入洞察了控制其热稳定性、熔化行为和光物理性质的结构-性质关系。我们的研究揭示了阳离子性质与由此产生的相变之间的系统相关性。此外，详细的光物理表征表明，某些衍生物表现出强烈的荧光，量子产率高达42%，这表明其在光电器件中有潜在应用。这些具有可调性质的热稳定有机离子材料具有广泛的潜在应用，从对热要求苛刻的环境（热响应材料、先进核反应堆冷却剂和热能存储）到利用其独特光致发光特性的光电器件。
