The inclusion of cobalt complexes in layers of ruthenium complexes can be used to control the electron-transfer pathways between the metal-oxide surfaces and the nanoscale layers of isostructural iron complexes. These iron complexes are positioned >70 nm from the electrode surfaces and can be fully insulated or electrochemically addressed, dependent on the ratio between the cobalt and ruthenium complexes. The different compositions and electrochemical properties are reflected in the intensities of the colors of these materials. Interestingly, the potential of these assemblies for energy storage and conversion was conceptually demonstrated by the efficient release of the electrochemically stored charge in the layers of the iron complexes. During the past two decades, several interesting studies debated the mechanism of electron transfer in structurally related metallo-organic films. The release of the trapped charges at the film-solution interfaces might indicate that an electron hopping or a stepping-stone mechanism can play an important role (rather than a diffusion-controlled mechanism). Furthermore, the solution-to-surface assembly of the mixtures of cobalt and ruthenium complexes results in films with compositions that do not reflect the molecular ratios in solution. The amount of ruthenium complex 1 is lower in the assembly than in solution, simultaneously the amount of cobalt complex 2 is higher in the assembly. Although the distance between these centrally positioned cations and the coordination sites for palladium is >1.0 nm, a noticeable long-range effect was induced by the metal centers. This observation shows that the formation of such films is not trivial, and currently, the parameters that control the composition are unknown. However, the combination of just two layers of three isostructural metal complexes in different ratios resulted in a series of conceptually new functional materials.