The transient species formed by oxidation of three dimers of 5,6-dihydroxyindole (1), a major building block of the natural biopolymer eumelanin, have been investigated. Pulse radiolytic oxidation of 5,5',6,6'-tetrahydroxy-2,4'-biindolyl (3) and 5,5',6,6'-tetrahydroxy-2,7'-biindolyl (4) led to semiquinones absorbing around 450 nm, which decayed with second-order kinetics (2k = 2.8 x 10(9) and 1.4 x 10(9) M-1 s(-1), respectively) to give the corresponding quinones (500-550 nm). 5,5', 6, 6'-Tetrahydroxy-2,2'-biindolyl (2), on the other hand, furnished a semiquinone (lambda(max) = 480 nm) which disproportionated at a comparable rate (2k = 3 x 10(9) M-1 s(-1)) to give a relatively stable quinone (lambda(max) = 570 nm). A quantum mechanical investigation of o-quinone, quinonimine, and quinone methide structures of 2-4 suggested that oxidized 2-4 exist mainly as 2-substituted extended quinone methide tautomers. Finally, an oxidation product of 3 was isolated for the first time and was formulated as the hydroxylated derivative 5 arising conceivably by the addition of water to the quinone methide intermediate predicted by theoretical analysis. Overall, these results suggest that the oxidation chemistry of biindolyls 2-4 differs significantly from that of the parent 1, whereby caution must be exercised before concepts that apply strictly to the mode of coupling of 1 are extended to higher oligomers.