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Abstract Effective photoinduced charge transfer makes molecular bimetallic assemblies attractive for applications as active light‐induced proton reduction systems. Developing competitive base metal dyads is mandatory for a more sustainable future. However, the electron transfer mechanisms from the photosensitizer to the proton reduction catalyst in base metal dyads remain so far unexplored. A Fe─Co dyad that exhibits photocatalytic H2 production activity is studied using femtosecond X‐ray emission spectroscopy, complemented by ultrafast optical spectroscopy and theoretical time‐dependent DFT calculations, to understand the electronic and structural dynamics after photoexcitation and during the subsequent charge transfer process from the FeII photosensitizer to the cobaloxime catalyst. This novel approach enables the simultaneous measurement of the transient X‐ray emission at the iron and cobalt K‐edges in a two‐color experiment. With this methodology, the excited state dynamics are correlated to the electron transfer processes, and evidence of the Fe→Co electron transfer as an initial step of proton reduction activity is unraveled.

Abstract Single‐ion magnets (SIMs) constitute the ultimate size limit in the quest for miniaturizing magnetic materials. Several bottlenecks currently hindering breakthroughs in quantum information and communication technologies could be alleviated by new generations of SIMs displaying multifunctionality. Here, ultrafast optical absorption spectroscopy and X‐ray emission spectroscopy are employed to track the photoinduced spin‐state switching of the prototypical complex [Co(terpy)2]2+ (terpy = 2,2′:6′,2″‐terpyridine) in solution phase. The combined measurements and their analysis supported by density functional theory (DFT), time‐dependent‐DFT (TD‐DFT) and multireference quantum chemistry calculations reveal that the complex undergoes a spin‐state transition from a tetragonally elongated doublet state to a tetragonally compressed quartet state on the femtosecond timescale, i.e., it sustains ultrafast Jahn‐Teller (JT) photoswitching between two different spin multiplicities. Adding new Co‐based complexes as possible contenders in the search for JT photoswitching SIMs will greatly widen the possibilities for implementing magnetic multifunctionality and eventually controlling ultrafast magnetization with optical photons.