Sulfate donor based supramolecular coordination complexes [{fac-Re(CO)(3)}(mu-SO4)(L-n)(2) {fac-Re(CO)(3)}] (1-3) were obtained using ditopic N donors (L-n; n = 1-3), NaHSO3, and Re-2(CO)(10) in a one-pot, multicomponent, coordination-driven self-assembly approach, in which SO32- becomes oxidized to SO42- during the reaction and acts as a building framework. Complexes 1-3 were characterized using IR, ESI-TOF-MS, and H-1 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)(3) Cl}(2) (L-n)(2)] = L-1, L-2, L-3; 4a-6a) was achieved by the addition of BaCl2. The direct treatment of Re(CO)(5)X (X = CI, Br) with L-1/L-2/L-3 yielded the dinuclear homoleptic doublestranded helicates [{Re(CO)(3)X}(2) (L-n)(2)] (4b-6b and 7-9).