Abstract: Cubane-type iron-sulfur clusters are some of nature’s most ancient and versatile cofactors. However, seemingly simple, their main function is electron transfer, that can be coupled to proton transfers. While being ubiquitous in enzymatic systems, a few significant functions remained to be modeled using synthetic molecular mimics. In this talk, we will introduce the use of synthetic Fe₄S₄ clusters acting as concerted proton electron transfer (CPET) mediators for electrocatalytic metal hydride generation, exploited in the context of CO₂ reduction.Further exploring bio-inspired strategies for electron transfers and storage, we will report here the preparation of the first complete redox series of Fe₄S₄ complexes that covers all oxidation states accessible by one-electron transformations of the individual Fe-atoms ([Fe₄S₄]⁴⁺-[Fe₄S₄]⁰). The redox potential of Fe₄S₄ cubanes is often conceived as a static parameter, which fails to explain some of Nature’s more elaborate electron transfer mechanisms, particularly conformationally gated ones. Further replicating the modulation of electric fields in enzymatic systems with our synthetic models, we will present here the case of a synthetic Fe₄S₄(SR)₄ model complex exhibiting dynamic redox potentials on-demand. This can be used to control the occurrence of formerly “uphill” electron transfers similar to these observed in Fe₄S₄-containing ATPases, archerases.