Electron-transfer (ET) reactions from aromatic amines to excited states of rhenium(I)-based molecular rectangles [{Re(CO)(3)(mu-bpy)Br}{Re(CO)(3)(mu-L)Br}](2) (bpy = 4,4'-bipyridine, L = 4,4'-dipyridylacetylene (dpa), I; L = 4,4'-dipyridylbutadiyne (dpb), II; and L = 1,4-bis(4'-pyridylethynyl)benzene (bpeb), III) were investigated in a dichloromethane solution using luminescence quenching techniques. Direct evidence for the ET reaction was obtained from the detection of the amine cation radical in this system using time-resolved transient absorption spectroscopy. The values of the luminescence quenching rate constants, k(q), of the (MLCT)-M-3 excited state of Re(I) rectangles with amines were found to be higher than those for the monomeric Re(I) complexes and other Re(I)-based metallacyclophanes. The observed k(q) values were correlated well with the driving force (Delta G degrees) for the ET reactions. In addition, a semiclassical theory of ET was successfully applied to the photoluminescence quenching of Re(I) rectangles with amines.