Melt-quenched porous organic cage glasses
Melt-quenched porous organic cage glasses
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DOI：
10.1039/d1ta01906f
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发表时间：
2021-05-04
影响因子：
11.9
通讯作者：
Greenaway, Rebecca L.
中科院分区：
文献类型：
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作者：
Brand, Michael C.;Greenwell, Francesca;Greenaway, Rebecca L.
多孔有机笼（POC）的离散分子性质使我们能够通过晶体工程指导晶体材料的形成。还可以通过化学改性或加工故意破坏晶体堆积来制造多孔无定形固体。最近，有机笼被用来形成各向同性多孔液体。然而，POC 的固态和液态以及玻璃态之间的联系几乎完全未被探索。在这里，我们研究了一系列有机笼的熔化和玻璃形成行为，包括通过亚胺缩合形成的形状持久性POC，以及更灵活且缺乏形状持久性的还原和合成后改性的胺POC。有机笼表现出熔化并淬灭所得液体，提供分子玻璃。与起始无定形笼相比，其中一种分子玻璃对 CO2 和 CH4 的气体吸收率有所提高。此外，在一种情况下，液体发泡会产生更稳定且溶解度更低的玻璃，这表明了无需溶液处理即可形成膜等材料的替代方法的潜力。
The discrete molecular nature of porous organic cages (POCs) has allowed us to direct the formation of crystalline materials by crystal engineering. It has also been possible to create porous amorphous solids by deliberately disrupting the crystalline packing, either with chemical modification or by processing. More recently, organic cages were used to form isotropic porous liquids. However, the connection between solid and liquid states of POCs, and the glass state, are almost completely unexplored. Here, we investigate the melting and glass-forming behaviour of a range of organic cages, including both shape-persistent POCs formed by imine condensation, and reduced and synthetically post-modified amine POCs that are more flexible and lack shape-persistence. The organic cages exhibited melting and quenching of the resultant liquids provides molecular glasses. One of these molecular glasses exhibited improved gas uptake for both CO2 and CH4 compared to the starting amorphous cage. In addition, foaming of the liquid in one case resulted in a more stable and less soluble glass, which demonstrates the potential for an alternative approach to forming materials such as membranes without solution processing.