State Key Laboratory of Materials Processing and Die & Mold Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, China.
Department of Chemistry, The University of Texas at Austin, Austin, Texas 78712-1224, United States.
J Am Chem Soc. 2021 Nov 17;143(45):18849-18853. doi: 10.1021/jacs.1c09385. Epub 2021 Nov 8.
The use of molecular crystalline materials for the separation and purification of chemical raw materials, particularly polar compounds with similar physical and chemical properties, represents an ongoing challenge. This is particularly true for volatile feedstocks that form binary azeotropes. Here we report a new cavity-extended version of calix[4]pyrrole () that readily forms nonporous adaptive crystals (NACs). These -based NACs allow pyridine to be separated from toluene/pyridine mixtures with nearly 100% purity, as well as the removal of 1,4-dioxane from 1,4-dioxane/water mixtures with high adsorption capacity. Removal of the polar guest (pyridine or 1,4-dioxane) from the guest-loaded NACs by heating under vacuum produces the guest-free crystalline form. In the case of both guests, the material could be reused as demonstrated through 10 uptake and release cycles without apparent performance loss.
利用分子晶体材料对化学原料进行分离和提纯，特别是对具有相似物理化学性质的极性化合物进行分离和提纯，这是一个持续存在的挑战。对于形成二元共沸物的挥发性原料来说，情况更是如此。在这里，我们报道了一种新型的空腔扩展型杯[4]吡咯（），它很容易形成无孔自适应晶体（NACs）。这些基于的 NACs 允许吡啶从甲苯/吡啶混合物中几乎以 100%的纯度分离出来，并且从 1,4-二氧六环/水混合物中以高吸附容量去除 1,4-二氧六环。通过在真空中加热将极性客体（吡啶或 1,4-二氧六环）从负载客体的 NACs 中去除，产生无客体的结晶形式。对于这两种客体，材料都可以通过 10 次吸收和解吸循环重复使用，而没有明显的性能损失。
