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

• Published in: Inorganic chemistry Vol. 64; no. 22; pp. 10933 - 10943
• Main Authors: Men, Xiao-Feng, Kong, Xiang-He, Huang, Zhi-Wei, Fu, Xuan, Mei, Lei, Niu, Na, Hu, Kong-Qiu, Shi, Wei-Qun
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 09.06.2025
• ISSN: 0020-1669; 1520-510X; 1520-510X
• DOI: 10.1021/acs.inorgchem.5c00969

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, (UO2)3(DMF)2(CO3)­(bmpd)·DMF (IHEP-34) and (UO2)10(O)2(OH)2(CO3)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 [(UO2)3(CO3)]4+ unit, whose configuration strikingly differs from the typical triangular [(UO2)3(O)]4+/[(UO2)3(OH)]5+ structures. Density functional theory calculations show that the [U3] cluster and [U10] cluster boast of remarkable stability with the HOMO–LUMO gap of 2.13 and 0.90 eV, respectively. The [U10] 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.