Exploration of mixed-valence chemistry: inventing new analogues of the Creutz-Taube ion.

Starting from the Creutz-Taube ion as the prototype of a molecule-bridged mixed-valent complex, a number of related systems are presented in which the metal, the co-ligands, the molecular bridge, the d electron configuration, the medium, the charge, the coordination mode, or the nuclearity have been modified. The new mixed-valent configurations, as obtained through various chemical approaches, display different stabilities and spectroscopic characteristics in relation to the Creutz-Taube ion; the analysis of these results serves to provide a better understanding of fundamental aspects of molecule-mediated metal-metal interaction.