Effective Uranyl Binding by a Dihydroxyazobenzene Derivative. Ionization of Uranium-Bound Water

In search of simple host molecules for uranyl ion which form 1: 1-type complexes with high formation constants that can be used either in extraction of uranium from seawater or in catalysis of biologically important organic reactions, the uranophile activities of dihydroxyazobenzene derivative 1 were studied. Uranyl ion and 1 form a 1: 1-type complex with a very large formation constant. The formation constant was measured at pH 7-11.6 by competition experiments with carbonate ion. From the resulting pH dependence, ionization constants of the two aquo ligands coordinated to the uranium of the uranyl complex of 1 were calculated. The ionization constants were also measured by potentiometric titration of the uranyl complex of 1. Based on these results, the pKa values of the two aquo ligands were estimated as 7.1 and 11.0, respectively. At pH 7.5-9.5, therefore, the complex exists mostly as monohydroxo species. Under the conditions of seawater, 1 possesses greater affinity toward uranyl ion compared with other uranophiles such as carbonate ion, calixarene derivatives, or a macrocyclic octacarboxylate. In addition, complexation of 1 with uranyl ion is much faster than that of the calixarene or octacarboxylate uranophiles.