Electroactive metallomacromolecules via tetrabis(2,2 ': 6 ',2 ''-terpyridine)ruthenium(II) complexes: Dendritic nanonetworks toward constitutional isomers and neutral species without external counterions

The concept of dendritic networks via four bis(2,2':6',2 " -terpyridine)rut henium(II connectivities was utilized to create "dendritic methane"-type me tallomacromolecules. In addition, two structurally isomeric metallodendrime rs (16 and 17) were designed, synthesized, and characterized. These two iso mers were spectrally alike and displayed very similar physical and chemical properties; however, the internal density and void regions of these molecu les were differentiated by cyclic voltammetry. The effects of the bulkiness of internal and external dendritic branches on the terpyridine-ruthenium c omplexes are described. A similar synthetic strategy allowed the preparatio n of two generations of neutral metallomacromolecules (33 and 36) pos ses s i ng no external counterions. The benefits of these internally charge-balan ced, neutral species are described, and the effects of increasing dendritic branching on their electrochemical behavior are detailed.