From sandwich complexes to dendrimers: journey toward applications to sensing, molecular electronics, materials...

This review links various areas of inorganic chemistry around the themes developed by our research group during the last four decades. It is firstly based on the electronic structure of iron sandwich complexes, showing how the metal electron count dictates their reactivities, with various applications (via C-H activation, C-C bond formation) as reducing and oxidizing agents, redox and electrocatalysts and precursors of dendrimers and catalyst templates through bursting reactions. Various electron-transfer processes and consequences are explored, including the influence of the redox state on the acidity of robust ligands and the possibility to iterate in situ C-H activation and C-C bond formation to build arene-cored dendrimers. Examples of how these dendrimers are functionalized are illustrated using the cross olefin metathesis reactions, with application to the synthesis of soft nanomaterials and biomaterials. Mixed and average valence complexes give rise to remarkable subsequent organometallic reactions, including the salt influence on these reactions. The stereo-electronic aspect of these mixed valencies is pointed out in star-shaped multi-ferrocenes with a frustration effect and other multi-organoiron systems, with the perspective of understanding electron-transfer processes among dendrimer redox sites involving electrostatic effects and application to redox sensing and polymer metallocene batteries. Dendritic redox sensing is summarized for biologically relevant anions such as ATP^2- with supramolecular exoreceptor interactions at the dendrimer periphery in parallel with the seminal work on metallocene-derived endoreceptors by Beer's group. This aspect includes the design of the first metallodendrimers that have applications in both redox sensing and micellar catalysis with nanoparticles. These properties provide the opportunity to summarize the biomedical (mostly anticancer) applications of ferrocenes, dendrimers and dendritic ferrocenes in biomedicine (in particular the contribution from our group, but not only). Finally, the use of dendrimers as templates for catalysis is illustrated with numerous reactions including C-C bond formation, click reactions and H₂ production reactions.