The concept of dendritic networks via four bis(2,2':6',2 " -terpyridine)ruthenium(II connectivities was utilized to create "dendritic methane"-type metallomacromolecules. In addition, two structurally isomeric metallodendrimers (16 and 17) were designed, synthesized, and characterized. These two isomers were spectrally alike and displayed very similar physical and chemical properties; however, the internal density and void regions of these molecules were differentiated by cyclic voltammetry. The effects of the bulkiness of internal and external dendritic branches on the terpyridine-ruthenium complexes are described. A similar synthetic strategy allowed the preparation of two generations of neutral metallomacromolecules (33 and 36) pos ses si ng no external counterions. The benefits of these internally charge-balanced, neutral species are described, and the effects of increasing dendritic branching on their electrochemical behavior are detailed.