Sulfate donor based supramolecular coordination complexes [{ fac-Re(CO)}(μ-SO)(L ){ fac-Re(CO)}] (1-3) were obtained using ditopic N donors (L ; n = 1-3), NaHSO, and Re(CO) in a one-pot, multicomponent, coordination-driven self-assembly approach, in which SO becomes oxidized to SO during the reaction and acts as a building framework. Complexes 1-3 were characterized using IR, ESI-TOF-MS, and H NMR spectroscopy. The structures of complexes 1-3 were confirmed using single-crystal X-ray diffraction analysis. The transformation of the dinuclear heteroleptic triple-stranded helicate to the dinuclear homoleptic double-stranded mesocate [{Re(CO)Cl}(L )] (L = L, L, L; 4a-6a) was achieved by the addition of BaCl. The direct treatment of Re(CO)X (X = Cl, Br) with L/L/L yielded the dinuclear homoleptic double-stranded helicates [{Re(CO)X} (L )] (4b-6b and 7-9).