Incongruent Melting and Vitrification Behaviors of Anionic Coordination Polymers Incorporating Ionic Liquid Cations
Incongruent Melting and Vitrification Behaviors of Anionic Coordination Polymers Incorporating Ionic Liquid Cations
复制标题
掺入离子液体阳离子的阴离子配位聚合物的不一致熔融和玻璃化行为
DOI：
10.1021/acs.inorgchem.2c02147
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发表时间：
2022
影响因子：
4.6
通讯作者：
Furushima Yoshitomo
中科院分区：
文献类型：
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作者：
Mochida Tomoyuki;Qiu Yi;Sumitani Ryo;Kimata Hironori;Furushima Yoshitomo
近年来，几种具有高柔韧性和可加工性的可熔融配位聚合物(CP)已被开发出来，但这些材料的熔融机理和玻璃化条件还不完全清楚。在本研究中，我们合成了含有离子液体组分的可熔性CPS[A][K(Tcm)2](A=阳离子，Tcm=C(CN)3-)，并详细研究了它们的晶体结构和熔融行为。这些CPS具有二维或三维的阴离子[K(Tcm)2]n-骨架，其中含有铀阳离子。每个CP在73-192°C的温度下发生不一致的熔融，生成离子液体([A][Tcm])和微晶钾[Tcm]的非均相混合物。此外，当进一步加热到∼240C时，它们形成均一液体。这些CP的熔点与其组成的离子液体的熔点呈线性相关。进一步研究了这些材料从熔融状态快速冷却时的玻璃化情况。玻璃化所需的冷却速度在不同的CP之间差异很大，并且与阳离子的柔韧性相关。
Several meltable coordination polymers (CPs) that possess substantial advantages attributable to their high flexibility and processability have been developed recently; however, the melting mechanism and vitrification conditions of these materials are not yet fully understood. In this study, we synthesized meltable CPs [A][K(TCM)2] (A = onium cation, TCM = C(CN)3–) incorporating ionic liquid components and investigated their crystal structures and melting behaviors in detail. These CPs feature two- or three-dimensional anionic [K(TCM)2]n–frameworks incorporating onium cations. Each CP was found to undergo incongruent melting at a temperature between 73 and 192 °C to produce a heterogeneous mixture of the ionic liquid ([A][TCM]) and microcrystalline K[TCM]. Furthermore, they formed homogeneous liquids upon further heating to ∼240 °C. The melting points of these CPs were linearly correlated with those of their constituent ionic liquids. The vitrification of these materials upon rapid cooling from the molten state was further investigated. The cooling rates required for vitrification differed greatly between the CPs and were correlated with the cation flexibility.