Controlling the Chirality of Metallo‐Cages by Manipulating the Stereochemistry of the Metal Centers

• Published in: Angewandte Chemie International Edition Vol. 64; no. 23; pp. e202503833 - n/a
• Main Authors: Li, Yu‐Qing, Fu, Lei, Jiang, Zhiyuan, Han, Ermeng, Li, Tian, Bai, Qixia, Xie, Ting‐Zheng, Zhang, Zhe, Wang, Pingshan, Wu, Tun
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 02.06.2025
• Edition: International ed. in English
• Subjects: Cages; Chiral induction; Chirality; Dynamics of metal ions; Handedness; Host–guest chemistry; Lability; Ligands; Metal ions; Metallography; Metallo‐cuboctahedra; Spontaneous resolution; Stereochemistry; Supramolecular compounds; Metallo‐cuboctahedra; Host–guest chemistry; Chiral induction; Dynamics of metal ions; Spontaneous resolution
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202503833

Precise control over the chirality of metallo‐cages by manipulating the stereochemistry of metal centers is important in many practical applications, but is extremely challenging. In this study, two isostructural metallo‐cuboctahedra (1‐ZnII12L18 and 2‐CdII12L18) have been assembled using ligand L1 and two kinds of metal ions (ZnII and CdII) with similar coordination lability. The chiral‐induction by the same guests (D‐/L‐camphorsulfonate, D‐/L‐SCS) results in a completely opposing stereochemical output of 1 and 2: D‐SCS induced host–guest complex of [D‐SCS⊂Δ12–1] and [D‐SCS⊂Λ12–2], respectively, with reverse handedness. The distinct stereochemical configuration of metallo‐cuboctahedra can be manipulated by participant metal ions that exhibit similar dynamics. Furthermore, a subtle variation of the ligand peripheral substituent group facilitates spontaneous resolution of metallo‐cuboctahedra 3‐ZnII12L28 from a racemic mixture as (R24, Λ12)‐3/(S24, Δ12)‐3 enantiopure entities. The dynamic stereochemistry of MII12L8 cuboctahedra described in this work allows a chiral manipulation based on the nature of metal centers and ligands, enabling the design and control of the chirality of metallo‐cages. Although the dynamics of ZnII and CdII ions are approximately the same, the stereochemistry of 1‐ZnII12L18 and 2‐CdII12L18 cuboctahedra induced by the same chiral guests (D‐/L‐camphorsulfonate) was opposite, thus enabling manipulation of the chirality of the metallo‐cages through the metal ions. Spontaneous resolution of 3‐ZnII12L28 into enantiopure individual crystals was achieved by changing the ligand's substituent to 2‐methylphenylethyl.