The uranyl(V) complexes [UO(dbm)K(18C6)] (dbm = dibenzoylmethanate) and [UO(L)](L = 2-(4-tolyl)-1,3-bis(quinolyl)malondiiminate), exhibiting diamond-shaped UO and triangular-shaped UO cores respectively with 5f-5f and 5f-5f-5f configurations, have been investigated using relativistic density functional theory (DFT). The bond order and QTAIM analyses reveal that the covalent contribution to the bonding within the oxo cores is slightly more important for UO than for UO, in line with the shorter U-O distances existing in the trinuclear complex in comparison to those in the binuclear complex. Using the broken symmetry (BS) approach combined with the B3LYP functional for the calculation of the magnetic exchange coupling constants () between the magnetic centers, the antiferromagnetic (AF) character of these complexes was confirmed, the estimated values being respectively equal to -24.1 and -7.2 cm for the dioxo and trioxo species. It was found that the magnetic exchange is more sensitive to small variations of the core geometry of the dioxo species in comparison to the trioxo species. Although the robust AF exchange coupling within the UO cores is generally maintained when small variations of the UOU angle are applied, a weak ferromagnetic character appears in the dioxo species when this angle is higher than 114°, its value for the actual structure being equal to 105.9°. The electronic factors driving the magnetic coupling are discussed.