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Chinese Journal of Organic Chemistry >

2014 , Vol. 34 >Issue 8: 1652 - 1661

DOI: https://doi.org/10.6023/cjoc201402033

Articles

Backbone Effect of Macrocycle Host Compound as Anion Receptor

  • Wei Jinyan ,
  • Xu Lijin ,
  • Gong Hanyuan
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  • a Department of Chemistry, Renmin University of China, Beijing 100872;
    b College of Chemistry, Beijing Normal University, Beijing 100875

Received date: 2014-02-27

  Revised date: 2014-03-12

  Online published: 2014-04-10

Supported by

Project supported by the National Natural Science Foundation of China (Nos. 21202199, 21372258).

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Abstract

Two novel macrocycle hosts with flexible frameworks and cavities, cyclo[2](2,6-di(1H-imidazol-1-yl)pyridine)[2] (1,4-dimethylenebenzene) (14+) and cyclo[2](2,6-di(1H-imidazol-1-yl)pyridine)[2](1,2-dimethylenebenzene) (24+), were synthesized with high yields via cyclization reactions between 2,6-di(1H-imidazol-1-yl)pyridine and 1,4-bisbromomethyl benzene or 1,2-bisbromomethyl-benzene. Herein, the interactions between 14+ or 24+ and a series of inorganic anionic guests were studied in detail via the following methods: (1) 1H NMR spectroscopy in d6-DMSO solution; (2) electrospray ionization mass spectrometry (ESI-MS) in gas phase; (3) single crystal X-ray crystallography in solid state. It is noted that the anionic guest species has different shapes, namely anions with ball shapes like Cl-, Br-, I-; linear anion N3-; triangle or tetrahedron HSO4-. The study found that 14+ can bind more small inorganic anion species than macrocycle 24+. In addition, the result implied that when the inorganic anion guest acts as strong intermolecular hydrogen bond acceptor (i.e. anionic guest (A-) such as Cl-, or ), the associate constant (Ka) maintains Ka[24+·A-]3+>Ka[14+·A-]3+; on the contrary, when anionic guest A- (Br- or I-) is hard to form intermolecular hydrogen bonds but easy contribute to anion-π interaction, the association constants of the 1:1 (host:guest) complexes follow another trend (i.e. Ka[24+·A-]3+<Ka[14+·A-]3+ when A- is Br- or I-). It is suggested that the skeleton of macrocycle host 24+ well organize its four strong acidic imidazolium C—H bonds for effective small inorganic anion binding mainly via intermolecular hydrogen bonds; meanwhile the bigger cavity and longer distances between the strong acidic imidazolium C—H bonds of 14+ leads two possible results: (1) worse cooperation of its acidic C—H bonds weaken the intermolecular hydrogen bonding interactions for small anion complexation; (2) its more relax backbone has possible benefits of binding more anion guests. In summary, small distinctions of the backbones between 14+ and 24+ result in significantly different anion complexations, including stoichiometries, association constants, binding modes, etc. This finding will help to guide following macrocyclic anion receptor design and study.

Key words： macrocycle; backbone; non-covalent weak interactions; anion binding

Cite this article

Wei Jinyan , Xu Lijin , Gong Hanyuan . Backbone Effect of Macrocycle Host Compound as Anion Receptor[J]. Chinese Journal of Organic Chemistry, 2014 , 34(8) : 1652 -1661 . DOI: 10.6023/cjoc201402033

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