C−C Bond as Shuttle of Two Electrons in Intermolecular and Intramolecular Processes: A Theoretical Approach to Molecular Batteries

Abstract

Density functional calculations have been carried out on titanium Schiff base complexes and titanium porphyrinogen complexes in order to understand the behavior of these systems in redox processes. In titanium Schiff base complexes CÀC s bonds are formed upon the acquisition of pairs of electrons, while in titanium porphyrinogen complexes CÀC s bonds are formed upon the donation of pairs of electrons. In both systems, the formation or the breaking of CÀC bonds avoids a variation in the oxidation state of the metal. These CÀC bonds, therefore, act not only as electron reservoirs, but also as a buffer for the oxidation state of the metal.

On the non-innocence of “Nacnacs”: ligand-based reactivity in β-diketiminate supported coordination compounds

“…22,[31][32][33][34][91][92][93][94][95][96][97][98][99][100][101] In particular, an analogous phenomenon is observed in macrocyclic tretraazannulene complexes. 22,[31][32][33][34][91][92][93][94][95][96][97][98][99][100][101] In particular, an analogous phenomenon is observed in macrocyclic tretraazannulene complexes.…”

Electrochromics by Intramolecular Redox Switching of Single Bonds

“…[15±18] Of course, reversible single-bond formation of appropriate radicals or radical ions should be enhanced and side reactions suppressed if the (formal) intermolecular dimerization is turned into an intramolecular reaction. This approach has already been verified for certain quinone methides (reduction), [19] metal complexes (reduction), [20,21] octamethoxytetraphenylene (oxidation), [22] and heterocycles connected to ring systems (oxidation [23±25] and reduction [26] ). We now extend this structural principle in two versions to electrochromics, which are characterized by strong differences in the light absorption of the reduced and oxidized states.…”

Controlling the nucleophilic properties of cobalt salen complexes for carbon dioxide capture

“…The stabilization of the complex resembles a metal-to-ligand charge transfer occurring in the nucleophilic attack of Co to the electrophilic carbon. [27][28][29]…”