By using electrochemical and spectroscopic techniques, we have investigated the interactions between the metal sites and the conjugated ligands in neutral and oxidized dinuclear ruthenium-acetylide derivatives. We have paid particular attention to the influence of the nature of the conjugated organic linking groups on the coupling strength between the metals, which determines the electrochemical properties of the complexes. On the basis of the experimental results, we propose a simple model to describe the oxidation process that is confirmed by semi-empirical quantum-chemical calculations.