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Homo-dinuclear nonlinear complexes [{M(dppe)Cp*}2{μ-(-CC)2X}] (dppe = 1,2-bis(diphenylphosphino)ethane; Cp* = η5-C5Me5; X = triphenylamine (TPA), M = Ru (1a) and Fe (1b); X = N,N,N′,N′-tetraphenylphenylene-1,4-diamine (TPPD), M = Ru (2a)) were prepared and characterized by 1H, 13C, and 31P NMR spectroscopy and single-crystal X-ray diffraction (1a, 2a). Attempts to prepare the diiron analogue of 2awere not successful. Experimental data obtained from cyclic voltammetry, square wave voltammetry, UV–vis–NIR (NIR = near-infrared) spectro-electrochemistry, and very informative IR spectro-electrochemistry in the CC stretching region, combined with density functional theory calculations, afford to make an emphasizing assessment of the close association between the metal–ethynyl termini and the oligophenylamine bridge core as well as their respective involvement in sequential one-electron oxidations of these complexes. The anodic behavior of the homo-bimetallic complexes depends strongly both on the metal center and the length of the oligophenylamine bridge core. The poorly separated first two oxidations of diiron complex 1bare localized on the electronically nearly independent Fe termini. In contrast, diruthenium complex 1aexhibits a significantly delocalized character and a marked electronic communication between the ruthenium centers through the diethynyl–TPA bridge. The ruthenium–ethynyl halves in 2a, separated by the doubly extended and more flexible TPPD bridge core, show a lower degree of electronic coupling, resulting in close-lying first two anodic waves and the NIR electronic absorption of [2a]+with an indistinctive intervalence charge transfer character. Finally, the third anodic waves in the voltammetric responses of the homo-bimetallic complexes are associated with the concurrent exclusive oxidation of the TPA or TPPD bridge cores.