This study presents the first report of an inherently chiral prismarene with resolved enantiomers. Prism[4]arenes, synthesized via a thermodynamic template approach using a tailor-made selective cation, effectively maintain their chirality due to their strained macrorings and narrow annuli, which prevent the flipping of naphthalene rings. The solid-state structure of the synthesized PrS[4]^iPe revealed a racemic crystal composed of all-pR and all-pS enantiomeric pairs, forming supramolecular polymeric chains of homochiral molecules interlinked by intermolecular host–guest interactions. Both enantiomers were resolved by using chiral high-performance liquid chromatography (HPLC), and their chiroptical properties were thoroughly investigated. Configurational assignment was achieved through time-dependent density functional theory (TDDFT) computations alongside electronic circular dichroism/ultraviolet–visible (ECD/UV–vis) spectral analysis. Notably, the circularly polarized luminescence (CPL) properties exhibited a significant dissymmetry ratio of 0.008 for these prism[4]arenes, due to electric and magnetic dipole transition moments both directed along the cylinder axis. Furthermore, the ability of PrS[4]^iPe to achieve enantioselective recognition with chiral ammonium guests was demonstrated.

中文翻译：

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介绍棱镜[4]芳烃：一种具有对映体可分辨固有手性和有趣的手性特性的大环

本研究首次报道了具有分离对映异构体的固有手性棱柱芳烃。棱柱[4]芳烃，通过使用定制的选择性阳离子的热力学模板方法合成，由于其应变的大环和狭窄的环，有效地保持了它们的手性，从而防止了萘环的翻转。合成的 PrS[4]^iPe 的固态结构揭示了由 all-pR 和 all-pS 对映体对组成的外消旋晶体，形成通过分子间主客体相互作用相互连接的同手性分子的超分子聚合物链。两种对映异构体均采用手性高效液相色谱 （HPLC） 分离，并对其手性特性进行了深入研究。构型分配是通过时间依赖性密度泛函理论 （TDDFT） 计算以及电子圆二色性/紫外-可见光 （ECD/UV-vis） 光谱分析实现的。值得注意的是，由于电和磁偶极子跃迁矩都沿圆柱轴定向，这些棱柱[4]芳烃的圆偏振发光 （CPL） 特性表现出 0.008 的显着不对称比。此外，证明了 PrS[4]^iPe 与手性铵客体实现对映选择性识别的能力。