Thermodynamic, Spectroscopic, and Structural Study on a Sodium Uranyl Tri-2-Methoxybenzoate Dodecahydrate Coordination Compound with Considerably Low Solubility in Acidic Conditions.

Abstract

A spontaneous crystallization of an uranium(VI)-organic coordination compound with sodium and 2-methoxybenzoate (2-mba) was observed in acidic solutions, and the solubility product, molecular vibrations, crystal structure, thermal stability, and emission properties of the atypically low-soluble U(VI) complex (Na[UO2(2-mba)3]·12H2O(s)) were fully investigated for the first time. A long-term solubility experiment and speciation modeling gave a solubility product of log Ks,0 = -12.18 ± 0.02 (T = 25 °C and I = 0.1 M NaClO4), and vibrational analyses confirmed the overall molecular structure of complex and the frequencies of characteristic stretching motions of uranyl moiety as well. The crystal quality of Na[UO2(2-mba)3]·12H2O(s) was improved by a digestion method, and X-ray diffraction analysis of the single crystalline specimen verified that the newly studied uranyl-organic compound contains one-dimensional channels with a diameter of 20 Å along the [001] direction; the sodium and water molecules are arranged in the channel structures. In the coordination environment around uranyl, three aromatic carboxylates are symmetrically bound in the equatorial plane of uranyl coplanarily, and the unit [UO2(2-mba)3]- complexes are further extended along the plane to form the layered-morphologies. The three-dimensional packing of [UO2(2-mba)3]- anions is driven by the parallel-displaced π-stacking of aromatic rings with a centroid-centroid distance of 3.7 Å. Additional thermogravimetric analysis confirmed that the Na[UO2(2-mba)3]·12H2O(s) is stable up to 250 °C, and dehydration and release of the organic ligand were subsequently observed beyond that temperature. Photoluminescence spectrum of the Na[UO2(2-mba)3]·12H2O(s) clearly displayed the characteristic U(VI) emission, and a band spacing between the ground electronic states of U(VI) uranyl was evaluated to be 831 ± 14 cm-1. Such detailed characterization of the unique Na[UO2(2-mba)3]·12H2O(s) is advancing upon a systematic understanding of the structural effects of the aromatic model ligands on U(VI) complexation, with relevance to the environmental chemistry of U(VI) and crystal engineering for development of diverse uranyl-organic frameworks.