We have designed a divergent synthetic strategy, based on the ''complexes-as-metals and complexes-as-ligands'' procedure, to prepare polynuclear metal compounds of nanometer size and dendritic structure. Such a synthetic strategy is modular, very flexible, efficient, and characterized by a full, step-by-step control of the growing process. It allows us to obtain supramolecular arrays where different metal ions, bridging ligands, and terminal ligands can occupy predetermined sites. In this way, the light absorption, luminescence, and redox properties of these polynuclear compounds can be varied. In particular, it is possible to obtain a synthetic control of the direction(s) of electronic energy transfer after light absorption. This is a step towards the construction of nanometer-sized antennae for harvesting solar energy.