期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 84, 期 5, 页码 2808-2816出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.joc.8b03197
关键词
-
资金
- NSF [CHE1708240]
Synthetic receptors that recognize ion pairs are potentially useful for many technical applications, but to date there has been little work on selective recognition of quaternary ammonium (Q(+)) ion pairs. This study measured the affinity of a tetralactam macrocycle for 11 different Q(+)Cl(-) salts in chloroform solution. In each case, NMR spectroscopy was used to determine the association constant (K-a) and the structure of the associated complex. K-a was found to depend strongly on the molecular shape of Q(+) and was enhanced when Q(+) could penetrate the macrocycle cavity and engage in attractive noncovalent interactions with the macrocycles NH residues and aromatic sidewalls. The highest measured K-a of 7.9 x 103 M-1 was obtained when Q(+) was a p-CN-substituted benzylic trimethylammonium. This high-affinity Q(+)Cl(-) ion pair was used as a template to enhance the synthetic yield of macrocyclization reactions that produce the tetralactam receptor or structurally related derivatives. In addition, a permanently interlocked rotaxane was prepared by capping the end of a noncovalent complex composed of the tetralactam macrocycle threaded by a reactive benzylic cation. The synthetic method provides access to a new family of rotaxanated ion pairs that can likely act as anion sensors, molecular shuttles, or transport molecules.
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