Controlling the Chirality of Metallo‐Cages by Manipulating the Stereochemistry of the Metal Centers
Abstract
AbstractPrecise 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.
Article Details
Authors (10)
Yu‐Qing Li
Hunan Key Laboratory of Micro & Nano Materials Interface Science College of Chemistry and Chemical Engineering Central South University Changsha 410083 China
Lei Fu
Department of Materials Process Engineering, Graduate School of Engineering, Nagoya University, Furu-cho, Chikusa-ku, Nagoya 464-8603, Japan
Zhiyuan Jiang
Department of Chemistry
Ermeng Han
Hunan Key Laboratory of Micro & Nano Materials Interface Science College of Chemistry and Chemical Engineering Central South University Changsha 410083 China
Tian Li
Qixia Bai
College of Environmental Science and Engineering
Ting‐Zheng Xie
Institute of Environmental Research At Greater Bay Area Key Laboratory for Water Quality and Conservation of the Pearl River Delta Ministry of Education Guangzhou Key Laboratory For Clean Energy and Materials Guangzhou University Guangdong China
Zhe Zhang
Pingshan Wang
Institute of Environmental Research at Greater Bay Area, Key Laboratory for Water Quality and Conservation of the Pearl River Delta, Ministry of Education, Guangzhou Key Laboratory for Clean Energy and Materials
Tun Wu
Department Institute of Environmental Research at Greater Bay Area, Key Laboratory for Water Quality and Conservation of the Pearl River Delta, Ministry of Education Institution Guangzhou University Guangzhou 510006 China