Spin‐State and Clustering Effects in Fe‐Complex Negolytes for Near‐Neutral Aqueous Redox Flow Batteries

Cost‐effective redox‐active materials are essential for advancing redox flow batteries (RFBs). Iron, with its abundance and suitability as a redox couple, is a promising candidate; however, achieving stable and fast redox reactions in aqueous RFBs remains a challenge. This study presents an Fe‐based negolyte stabilized by a hexadentate ligand, where Fe–ligand bonds are enhanced through intermolecular interactions. The sulfonate‐substituted Fe complex exhibits a formal potential of –0.44 V vs. Ag/AgCl and an exceptionally high rate constant of 0.69 cm s–1. Near‐neutral RFBs incorporating 0.5 M Fe complex show excellent cycling stability, with no discernable capacity fading over 300 cycles. This performance is attributed to intermolecular hydrogen bonds that reinforce Fe–ligand coordination and promote the formation of stable trimeric clusters. Operando electrochemical Raman spectroscopy and density functional theory reveal that π‐backdonation from Fe(II) to the imino‐phenolate moiety further stabilizes the complex after reduction. In contrast, the hydroxyl‐substituted complex exhibits inferior stability due to weaker hydrogen bonding and less pronounced π‐backdonation. These findings underscore the importance of ligand design and intermolecular interactions in developing cost‐effective, high‐performance redox‐active materials for aqueous RFBs.