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Macrocycle‐Directed Construction of Tetrahedral Anion–π Receptors for Nesting Anions with Complementary Geometry
Author(s) -
Luo Jian,
Zhu Jun,
Tuo DeHui,
Yuan Qinqin,
Wang Lei,
Wang XueBin,
Ao YuFei,
Wang QiQiang,
Wang DeXian
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201903272
Subject(s) - tetrahedron , crystallography , ion , chemistry , tetrahedral molecular geometry , coordination geometry , crystal structure , stereochemistry , molecule , hydrogen bond , organic chemistry
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.