Herein, we report that the introduction of fluorine binding sites to macrocycles achieves high-resolution gas chromatographic separation of aromatic hydrocarbons, cycloolefins, and cycloparaffins. The tetrafluoroterphen[3]arene (4FTP3) macrocycle, containing 12 fluorines on its skeleton edge, was synthesized in a 52% yield via a one-pot approach and then coated onto a capillary column as a gas chromatographic stationary phase. The resulting column permitted the high-resolution separation of cyclohexane/cyclohexene/benzene, cycloheptane/cycloheptene, and tetrahydronaphthalene/naphthalene mixtures, with a retention capacity decreasing in the order of aromatic hydrocarbons > cycloolefins > cycloparaffins. Single-crystal structural analysis revealed that 4FTP3 assembled into a three-dimensional superstructure with multiple internal cavities and external voids by multiple intermolecular C–H···F interactions and contributed to the separation. Significantly, the distinction of C–H···F interactions between macrocycle 4FTP3 and analytes resulted in different binding affinities, association enthalpies, and retention times for the various analytes and therefore plays a key role in such high-resolution separation. The simple preparation, high yield, and clear separation mechanism associated with 4FTP3 render it a cost-effective separation material for use in further applications. The design of macrocycles with specific binding sites provides new insights into high-resolution gas chromatographic separation.

中文翻译：

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合成氟边大环促进高分离度气相色谱分离


在此，我们报道了将氟结合位点引入大环循环实现了芳烃、环烯烃和环链烷烃的高分辨率气相色谱分离。四氟三苯[3]芳烃 （4FTP3） 大环的骨架边缘含有 12 个氟，通过一锅法以 52% 的收率合成，然后作为气相色谱固定相包被到毛细管柱上。所得色谱柱能够对环己烷/环己烯/苯、环庚烷/环庚烯和四氢萘/萘混合物进行高分离度分离，保留容量按芳烃 > 环烯烃 > 环链烷烃 > 环烷烃的顺序降低。单晶结构分析表明，4FTP3 通过多个分子间 C–H· 组装成具有多个内腔和外空隙的三维超结构F 相互作用并导致分离。值得注意的是，C–H···大环 4FTP3 与分析物之间的 F 相互作用导致各种分析物具有不同的结合亲和力、缔合焓和保留时间，因此在这种高分辨率分离中起着关键作用。与 4FTP3 相关的简单制备、高产率和清晰的分离机制使其成为一种经济高效的分离材料，可用于进一步的应用。具有特定结合位点的大环设计为高分辨率气相色谱分离提供了新的见解。