Redox Self-Equilibration in Molecular Vanadium Oxide Mixtures Enables Multi-Electron Storage.

Polyoxometalates (POMs) are ideal components for reversible multi-electron storage in energy technologies. To-date, most redox-applications employ only single, individual POM species, which limits the number of electrons that can be stored within a given potential window. Here, we report that spontaneous redox self-equilibration during cluster synthesis leads to the formation of two structurally related polyoxovanadates which subsequently aggregate into co-crystals.

Beyond the First Coordination Sphere─Manipulating the Excited-State Landscape in Iron(II) Chromophores with Protons.

Molecular transition metal chromophores play a central role in light harvesting and energy conversion. Recently, earth-abundant transition-metal-based chromophores have begun to challenge the dominance of platinum group metal complexes in this area. However, the development of new chromophores with optimized photophysical properties is still limited by a lack of synthetic methods, especially with respect to heteroleptic complexes with functional ligands.

Coupled reaction equilibria enable the light-driven formation of metal-functionalized molecular vanadium oxides.

The introduction of metal sites into molecular metal oxides, so-called polyoxometalates, is key for tuning their structure and reactivity. The complex mechanisms which govern metal-functionalization of polyoxometalates are still poorly understood. Here, we report a coupled set of light-dependent and light-independent reaction equilibria controlling the mono- and di-metal-functionalization of a prototype molecular vanadium oxide cluster.