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Uranyl Clusters Based on 1,10-Phenanthroline Derivative Ligands: Synthesis, Crystal Structures, and Iodine Capture

Year: 2025

Type: article

Abstract: The clusters have garnered widespread interest owing to their captivating structures and their potential applications in diverse scientific disciplines. Within this study, we synthesized two uranyl clusters, (UO 2 ) 3 (DMF) 2 (CO 3 )(bmpd)·DMF ( IHEP-34 ) and (UO 2 ) 10 (O) 2 (OH) 2 (CO 3 ) 2 (btpd) 2 ( IHEP-35 ), by the utilization of 1,10-phenanthroline derivative ligands in conjunction with uranyl cations through solvothermal synthesis techniques. Both clusters are characterized by a V-shaped [(UO 2 ) 3 (CO 3 )] 4+ unit, whose configuration strikingly differs from the typical triangular [(UO 2 ) 3 (O)] 4+ /[(UO 2 ) 3 (OH)] 5+ structures. Density functional theory calculations show that the [U 3 ] cluster and [U 10 ] cluster boast of remarkable stability with the HOMO–LUMO gap of 2.13 and 0.90 eV, respectively. The [U 10 ] clusters in IHEP-35 are orderly assembled through weak intermolecular interactions, forming a 3D supramolecular porous structure, which exhibits an excellent performance in the adsorption of gaseous iodine. The maximum adsorption capacity of IHEP-35 for gaseous iodine is 1324 mg·g –1 . The analysis of XPS and Raman spectra reveals that the adsorbed iodine in IHEP-35 predominantly exists in the form of a triiodide anion.

Source: Inorganic Chemistry

DOI: 10.1021/acs.inorgchem.5c00969