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Title: Macrocycle-Directed Construction of Tetrahedral Anion-pi Receptors for Nesting Anions with Complementary Geometry

Abstract

The unprecedented tetrahedral anion-? receptors have been successfully constructed by a macrocycle-directed approach. The use of large macrocycle precursors bearing four reaction sites enabled kinetic-favored cross-linking pathway and afforded 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 BF4-, ClO4-, H2PO4-, HSO4-, SO42- and PF6- has been observed by ESI-MS. Two complex crystal structures with ClO4- and PF6- demonstrated the anion was nicely encapsulated within the tetrahedral cavity through up to quadruple cooperative anion-? interactions by an excellent shape and size match. The favored complexation energies were established by DFT calculation and further confirmed by negative ion photoelectron spectroscopy study.

Authors:
 [1];  [1];  [1];  [2];  [2]; ORCiD logo [3];  [1];  [1];  [1]
  1. Chinese Academy of Sciences
  2. UNIVERSITY PROGRAMS
  3. BATTELLE (PACIFIC NW LAB)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1577056
Report Number(s):
PNNL-SA-143134
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 25; Journal Issue: 58
Country of Publication:
United States
Language:
English

Citation Formats

Luo, Jian, Zhu, Jun, Tuo, De-Hui, Yuan, Qinqin, Wang, Lei, Wang, Xue-Bin, Ao, Yu-Fei, Wang, Qiang Q., and Wang, De-Xian. Macrocycle-Directed Construction of Tetrahedral Anion-pi Receptors for Nesting Anions with Complementary Geometry. United States: N. p., 2019. Web. doi:10.1002/chem.201903272.
Luo, Jian, Zhu, Jun, Tuo, De-Hui, Yuan, Qinqin, Wang, Lei, Wang, Xue-Bin, Ao, Yu-Fei, Wang, Qiang Q., & Wang, De-Xian. Macrocycle-Directed Construction of Tetrahedral Anion-pi Receptors for Nesting Anions with Complementary Geometry. United States. doi:10.1002/chem.201903272.
Luo, Jian, Zhu, Jun, Tuo, De-Hui, Yuan, Qinqin, Wang, Lei, Wang, Xue-Bin, Ao, Yu-Fei, Wang, Qiang Q., and Wang, De-Xian. Thu . "Macrocycle-Directed Construction of Tetrahedral Anion-pi Receptors for Nesting Anions with Complementary Geometry". United States. doi:10.1002/chem.201903272.
@article{osti_1577056,
title = {Macrocycle-Directed Construction of Tetrahedral Anion-pi Receptors for Nesting Anions with Complementary Geometry},
author = {Luo, Jian and Zhu, Jun and Tuo, De-Hui and Yuan, Qinqin and Wang, Lei and Wang, Xue-Bin and Ao, Yu-Fei and Wang, Qiang Q. and Wang, De-Xian},
abstractNote = {The unprecedented tetrahedral anion-? receptors have been successfully constructed by a macrocycle-directed approach. The use of large macrocycle precursors bearing four reaction sites enabled kinetic-favored cross-linking pathway and afforded 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 BF4-, ClO4-, H2PO4-, HSO4-, SO42- and PF6- has been observed by ESI-MS. Two complex crystal structures with ClO4- and PF6- demonstrated the anion was nicely encapsulated within the tetrahedral cavity through up to quadruple cooperative anion-? interactions by an excellent shape and size match. The favored complexation energies were established by DFT calculation and further confirmed by negative ion photoelectron spectroscopy study.},
doi = {10.1002/chem.201903272},
journal = {Chemistry - A European Journal},
number = 58,
volume = 25,
place = {United States},
year = {2019},
month = {10}
}

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