Backbone Effect of Macrocycle Host Compound as Anion Receptor

doi:10.6023/cjoc201402033

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 (K_a) maintains K_a[2⁴⁺·A^-]³⁺>K_a[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. K_a[2⁴⁺·A^-]³⁺<K_a[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]. Chin. J. Org. Chem., 2014, 34(8): 1652-1661.

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