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Amphoteric Homotropic Allosteric Association between a Hexakis-Urea Receptor and Dihydrogen Phosphate
Seiya Kondo1, Junya Masuda1, Tomoki Komiyama1
1Department of Chemistry, Faculty of Science, Shizuoka University, 836 Ohya, Suruga-ku, Shizuoka, 422-8529, Japan.
Abstract:
Conformationally flexible hexakis-urea 1 was synthesized efficiently by condensing hexakis(aminomethyl)benzene with 4-nitrophenyl-(3,5-di-tert-butylphenyl)carbamate. The hexakis-urea 1 is unexpectedly soluble in organic solvents of low polarity due to intramolecular hydrogen bonding. The hexakis-urea 1 recognizes chloride, bromide, and acetate in a 1:2 host-guest ratio and in a positive allosteric manner in CDCl3 . The ability of 1 to recognize dihydrogen phosphate is a unique outcome, and the structure of the associated complex, which contains four dihydrogen phosphate ions, was clarified by single-crystal X-ray structural analysis. However, in solution, a complex with three dihydrogen phosphate ions was identified. The dihydrogen phosphate association in CDCl3 proceeds in an amphoteric allosteric manner; in a positive allosteric manner (K1
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