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Chirality Sensing of Cryptochiral Guests with Prism[n]arenes
Chemistry - A European Journal ( IF 4.3 ) Pub Date : 2024-05-08 , DOI: 10.1002/chem.202401625
PAOLO DELLA SALA 1 , Umberto Calice 2 , Veronica Iuliano 3 , Silvano Geremia 4 , Neal Hickey 4 , Sandra Belviso 2 , Francesco Ferdinando Summa 3 , Guglielmo Monaco 5 , Carmine Gaeta 3 , Stefano Superchi 2
Affiliation  

Optical chirality sensing has gained significant attention in recent years. Within this field, the quest for stereodynamic chiroptical probes capable of detecting cryptochiral guests presents a formidable challenge. Macrocycles exhibiting planar chirality have emerged as promising candidates for amplifying the chirality of cryptochiral guests. In this study, we demonstrate that the formation of host‐guest complexes between cryptochiral molecules and planar chiral prismarenes triggers electronic circular dichroism (ECD) signals via host‐guest complexation‐induced chirality amplification. The absolute configuration of the most stable chiral macrocyclic host‐guest complex has been established by resorting to both exciton model and DFT computations. Furthermore, we demonstrated that this supramolecular chirality sensing system can be employed to determine the enantiomeric composition of scalemic mixtures by measuring the ECD bands intensity. The information described here opens the way for the use of prismarenes as stereodynamic probes for sensing of cryptochiral guests.

中文翻译:

用棱镜[n]芳烃对隐手性客体进行手性传感

近年来,光学手性传感受到了广泛关注。在这一领域,寻找能够检测隐手性客体的立体动力学手性光学探针是一项艰巨的挑战。表现出平面手性的大环化合物已成为放大隐手性客体手性的有希望的候选者。在这项研究中,我们证明了隐手性分子和平面手性海藻烯之间形成的主客体复合物通过主客体络合诱导的手性放大触发了电子圆二色性(ECD)信号。通过激子模型和DFT计算,建立了最稳定的手性大环主客体配合物的绝对构型。此外,我们证明了这种超分子手性传感系统可用于通过测量 ECD 带强度来确定尺度混合物的对映体组成。这里描述的信息为使用棱柱石作为立体动力学探针来感应隐手性客体开辟了道路。
更新日期:2024-05-08
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