Wu Jia-Rui, Wu Gengxin, Li Dongxia, Dai Dihua, Yang Ying-Wei
International Joint Research Laboratory of Nano-Micro Architecture Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, P. R. China.
Key Laboratory of Automobile Materials of Ministry of Education and School of Materials Science and Engineering, Jilin University, 5988 Renmin Street, Changchun 130025, P. R. China.
Sci Adv. 2022 Jun 3;8(22):eabo2255. doi: 10.1126/sciadv.abo2255.
The separation of haloalkane isomers with distillation-free strategies is one of the most challenging research topics in fundamental research and also gave high guiding values to practical industrial applications. Here, this contribution provides a previously unidentified solid supramolecular adsorption material based on a leggero pillararene derivative , which can separate 1-/2-bromoalkane isomers with near-ideal selectivity. Activated solids of with interesting amorphous and nonporous features could adsorb 1-bromopropane and 1-bromobutane from the corresponding equal volume mixtures of 1-/2-positional isomers with purities of 98.1 and 99.0%, respectively. Single-crystal structures incorporating theoretical calculation reveal that the high selectivity originates from the higher thermostability of 1-bromoalkane-loaded structures compared to its corresponding isomer-loaded structures, which could be further attributed to the perfect size/shape match between and 1-bromoalkanes. Moreover, control experiments using its counterpart macrocycle of traditional pillararene demonstrate that has better adsorptive selectivity, benefiting from the intrinsic free-rotation phenylene subunit on its backbone.
采用无蒸馏策略分离卤代烷异构体是基础研究中最具挑战性的研究课题之一，对实际工业应用也具有很高的指导价值。在此，本文报道了一种基于轻柱芳烃衍生物的新型固体超分子吸附材料，该材料能够以近乎理想的选择性分离1-/2-溴代烷异构体。具有有趣的无定形和无孔特征的活化固体能够从相应等体积的1-/2-位置异构体混合物中吸附1-溴丙烷和1-溴丁烷，纯度分别为98.1%和99.0%。结合理论计算的单晶结构表明，高选择性源于负载1-溴代烷的结构比其相应的负载异构体的结构具有更高的热稳定性，这可进一步归因于[具体物质]与1-溴代烷之间完美的尺寸/形状匹配。此外，使用传统柱芳烃的对应大环进行的对照实验表明，[具体物质]具有更好的吸附选择性，这得益于其主链上固有的自由旋转亚苯基单元。
