Li Errui, Zhu Weijie, Fang Shuai, Jie Kecheng, Huang Feihe
Stoddart Institute of Molecular Science, Department of Chemistry, Zhejiang University, Hangzhou, 310027, P. R. China.
State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, P. R. China.
Angew Chem Int Ed Engl. 2022 Oct 10;61(41):e202211780. doi: 10.1002/anie.202211780. Epub 2022 Sep 8.
Postsynthetic modification (PSM) has been widely used in porous crystalline materials to gain better performance in adsorptive separation of gases or hydrocarbons. We here report that guest adsorption selectivity in a kind of nonporous crystalline materials, namely nonporous adaptive crystals (NACs), can be readily and precisely tuned via a facile substituent-size-dependent solid-vapor PSM method. Before PSM, NACs of pillar[4]arene[1]quinone EtP4Q1 show negligible selectivity for C hydrocarbons. PSM with a larger substituent, cyclopentylamine, onto EtP4Q1 NACs does not improve the selectivity, while EtP4Q1 NACs after PSM with a slightly smaller substituent, cyclobutylamine, is endowed with very high preference of n-pentane over cyclopentane. Comprehensive structural analyses confirm that the intermolecular interactions among the host compounds and host-guest interactions between the adsorbent and the adsorbate are the two major factors in determining the guest selectivity.
合成后修饰（PSM）已广泛应用于多孔晶体材料，以在气体或碳氢化合物的吸附分离中获得更好的性能。我们在此报告，通过一种简便的基于取代基大小的固-气PSM方法，可以轻松且精确地调节一种无孔晶体材料（即无孔自适应晶体，NACs）中的客体吸附选择性。在PSM之前，柱[4]芳烃[1]醌EtP4Q1的NACs对碳氢化合物的选择性可忽略不计。用较大的取代基环戊胺对EtP4Q1 NACs进行PSM并不能提高选择性，而用稍小的取代基环丁胺进行PSM后的EtP4Q1 NACs对正戊烷的选择性远高于环戊烷。综合结构分析证实，主体化合物之间的分子间相互作用以及吸附剂与被吸附物之间的主客体相互作用是决定客体选择性的两个主要因素。
