Dendritic Molecular Electrochromic Batteries Based on Redox‐Robust Metallocenes

In this Concept article, we summarize and discuss recent reports on dendritic molecular electrochromic batteries. Giant dendrimers containing 3(n+2) terminal tethers (n = generation number) and terminated by first-raw late-transition-metal metallocenes, permethyl metallocenes and other sandwich complexes were shown to be redox robust. Indeed, they can be oxidized and reduced without decomposition and exist under two stable oxidation states (Fe(III/II), Co(III/II)). Thus, a pre-determined number of electrons (up to 14,000) per dendrimer can be exchanged. Cyclic voltammetry showed a remarkable complete reversibility even up to 14,000 Fe and Co termini in metallodendrimers, indicating fast electron hoping among the redox sites and between dendrimers on a carbon surface covered by arylcarboxylate groups. The dendrimer sizes were measured by dynamic light scattering in solution and by AFM (subsequent to flattening in the condensed state also indicating that these metallodendrimers aggregate to form discrete nanoparticles of dendrimers, as atoms do). The metallodendrimer size varies considerably between the two redox forms due to tether extension of the cationic dendrimers upon oxidation, and a breathing mechanism was shown by atomic and electric force microscopy (AFM and EFM). When the redox potential is very negative, the reduced form is an electron-reservoir system that can deliver a large number of electrons per dendrimer to various reducible substrates. These systems are thus potential dendritic molecular batteries with two different colors for the two redox forms (electrochromic behavior).