Hierarchical amplification of chirality in anion-coordinated tetrahedral cages†

Jie Zhao , Mingli Lian , Zijian Ni , Le Yu , Dong Yang
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Abstract

Chirality is vital in asymmetric catalysis, biological systems, and materials science. However, the control of chiral transfer and amplification remains challenging, but fascinating. Herein, we report the chirality transferred from chiral carbon centers to ‘aniono’ tetrahedral cages, which were constructed through the self-assembly of chiral C3-symmetric tris–bis(urea) ligands and oxoanions (PO43− or CO32−). The host–guest interaction can further alter the chirality, resulting in enhanced CD intensity accompanied by a redshift. Furthermore, anions have a great influence on the chiral behavior of the mixed-ligand (chiral and achiral ligands mixed in different proportions) cages due to the occurrence of structural transformation. From the self-assembly and subsequent host–guest chemistry, we establish a hierarchical chiral system at the supramolecular level, featuring controllable chiral transfer and amplification.

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阴离子配位四面体笼中手性的分级放大
手性在不对称催化、生物系统和材料科学中至关重要。然而,手性转移和扩增的控制仍然具有挑战性,但令人着迷。本文报道了手性从手性碳中心转移到“阴离子”四面体笼上,该笼是通过手性c3对称三双(尿素)配体和氧阴离子(PO43−或CO32−)的自组装构建的。主客体相互作用可以进一步改变手性,导致CD强度增强并伴有红移。此外,阴离子由于结构转化的存在,对混合配体(手性和非手性配体按不同比例混合)笼的手性行为有很大的影响。通过自组装和随后的主客体化学,我们在超分子水平上建立了一个手性转移和扩增可控的层叠性手性体系。
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