Macrocycle‐Directed Construction of Tetrahedral Anion–π Receptors for Nesting Anions with Complementary Geometry

Journal Article · 24 September 2019 · Chemistry - A European Journal

DOI: https://doi.org/10.1002/chem.201903272 · OSTI ID:1566161

Luo, Jian ^[1]; Zhu, Jun ^[1]; Tuo, De‐Hui ^[1]; Yuan, Qinqin ^[2]; Wang, Lei ^[2]; Wang, Xue‐Bin ^[2]; Ao, Yu‐Fei ^[3]; Wang, Qi‐Qiang  ^[1]; Wang, De‐Xian  ^[1]

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1. Beijing National Laboratory for Molecular Sciences CAS Key Laboratory of Molecular Recognition and Function Institute of Chemistry Chinese Academy of Sciences Beijing 100190 P. R. China, University of Chinese Academy of Sciences Beijing 100190 P. R. China
2. Physical Sciences Division Pacific Northwest National Laboratory 902 Battelle Boulevard, P.O. Box 999, MS K8-88 Richland Washington 99352 USA
3. Beijing National Laboratory for Molecular Sciences CAS Key Laboratory of Molecular Recognition and Function Institute of Chemistry Chinese Academy of Sciences Beijing 100190 P. R. China

Abstract Manipulation of the emerging anion–π interactions in a highly cooperative manner through sophisticated host design represents a very challenging task. In this work, unprecedented tetrahedral anion–π receptors have been successfully constructed for complementary accommodation of tetrahedral and relevant anions. The synthesis was achieved by a macrocycle‐directed approach by using large macrocycle precursors bearing four reactive sites, which enabled a kinetic‐favored pathway and afforded the otherwise inaccessible tetrahedral cages in considerable yields. Crystal structure suggested that the tetrahedral cages have an enclosed three‐dimensional cavity surrounded by four electron‐deficient triazine faces in a tetrahedral array. The complementary accommodation of a series of tetrahedral and relevant anions including BF ₄ ⁻ , ClO ₄ ⁻ , H ₂ PO ₄ ⁻ , HSO ₄ ⁻ , SO ₄ ²⁻ and PF ₆ ⁻ was revealed by ESI‐MS and DFT calculations. Crystal structures of ClO ₄ ⁻ and PF ₆ ⁻ complexes showed that the anion was nicely encapsulated within the tetrahedral cavity with up to quadruple cooperative anion–π interactions by an excellent shape and size match. The strong anion–π binding was further confirmed by negative ion photoelectron spectroscopy measurements.

• Sponsoring Organization: USDOE
• OSTI ID: 1566161
• Journal Information: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 58 Vol. 25; ISSN 0947-6539
• Publisher: Wiley Blackwell (John Wiley & Sons)Copyright Statement
• Country of Publication: Germany
• Language: English