A Combined Spectroscopic and Theoretical Study on a Ruthenium Complex Featuring a π-Extended dppz Ligand for Light-Driven Accumulation of Multiple Reducing Equivalents.

The design of photoactive systems capable of storing and relaying multiple electrons is highly demanded in the field of artificial photosynthesis, where transformations of interest rely on multielectronic redox processes. The photophysical properties of the ruthenium photosensitizer [(bpy)2 Ru(oxim-dppqp)]2+ (Ru), storing two electrons coupled to two protons on the π-extended oxim-dppqp ligand under light-driven conditions, are investigated by means of excitation wavelength-dependent resonance Raman and transient absorption spectroscopies, in combination with time-dependent density functional theory; the results are discussed in comparison to the parent [(bpy)2 Ru(dppz)]2+ and [(bpy)2 Ru(oxo-dppqp)]2+ complexes. In addition, this study provides in-depth insights on the impact of protonation or of accumulation of multiple reducing equivalents on the reactive excited states.

Separating Cationic and Anionic Redox Activity in the Lithium-Rich Antiperovskite (Li2Fe)SO.

Lithium-rich antiperovskites promise to be a compelling class of high-capacity cathode materials due to the existence of both cationic and anionic redox activity. Little is however known about the effect of separating the electrochemical cationic process from the anionic process and the associated implications on the electrochemical performance. In this context, we report the electrochemical properties of the illustrative example of three different (Li2Fe)SO materials with a focus on separating cationic from anionic effects. With the high-voltage anionic process, an astonishing electrochemical capacity of around 400 mAh g-1 can initially be reached. Our results however identify the anionic process as the cause of poor cycling stability and demonstrate that the fading reported in previous literature is avoided by restricting to only the cationic processes. Following this path, our (Li2Fe)SO-BM500 shows strongly improved performance as indicated by constant electrochemical cycling over 100 cycles at a capacity of around 175 mAh g-1 at 1 C. Our approach also allows us to investigate the electrochemical performance of the bare antiperovskite phase excluding extrinsic activity from initial or cycling-induced impurity phases. Our results underscore that synthesis conditions are a critical determinant of electrochemical performance in lithium-rich antiperovskites, especially with regard to the amount of electrochemical secondary phases, while the particle size has not been found to be a crucial parameter. Overall, separating and understanding the effects of the cationic from the anionic redox activity in lithium-rich antiperovskites provides the route to further improve their performance in electrochemical energy storage.