Metallo‐Supramolecular Octahedral Cages with Three Types of Chirality towards Spontaneous Resolution. Issue 27 (12th May 2022)

• Record Type: Journal Article
• Authors: Xu, Chen; Lin, Quanjie; Shan, Chuan; Han, Xin; Wang, Hao; Wang, Heng; Zhang, Wenjing; Chen, Zhi; Guo, Chenxing; Xie, Yinghao; Yu, Xiujun; Song, Bo; Song, Heng; Wojtas, Lukasz; Li, Xiaopeng
• Is Part Of: Angewandte Chemie international edition. Volume 61:Issue 27(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-05-12
• Subjects: Chiral Octahedral Cages -- Chiral Self-Sorting -- Conglomerates -- Spontaneous Resolution -- Truxene; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202203099
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Chirality is one of the most important intrinsic properties of (supra)molecules. In this study, we obtained enantiomeric metallo‐supramolecular octahedra without using any chiral sources. Such cages were self‐assembled by prochiral trispyridine ligand L based on a C 3h truxene core and Cu II salts. Crystallization of the cages with BF4 − as counterions afforded racemate crystals; while crystallizations of cages with ClO4 − and OTf − as counterions resulted in conglomerates with spontaneous resolution. Three types of chirality were observed in each cage, including planar chirality of the truxene core, axial chirality from the pyridyl and truxene moieties, and propeller chirality of the pyridyl‐Cu II coordination sites. The cages reported here are among the largest discrete synthetic metallo‐supramolecules ever reported with chiral self‐sorting behavior. Remarkably, the chiral cages exhibited very slow racemization even at low concentrations, suggesting their high stability in solution. Abstract : Chiral metallo‐supramolecular octahedral cages were obtained as conglomerates with spontaneous resolution. During crystallization, anions play a critical role in formation of racemic compounds or conglomerates. Moreover, the enantiopure cages are very stable in solution, and exhibit slow racemization even at extremely low concentrations.