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.