Abstract:
While the central metal ion in molecular systems has conventionally been regarded as the primary driver of electrochemical activity, emerging evidence highlights the critical role of ligand nature and, notably, ligand isomerism in modulating electrochemical kinetics, mechanisms, and energy storage. This perspective discusses how molecular-scale structural variations in ligands influence interfacial dynamics and reaction pathways, often rivaling or surpassing metal-centered effects. These findings challenge conventional design strategies and emphasize the importance of considering ligand architecture as equally vital as the metal ion in molecular electrochemistry. A deeper understanding of these ligand effects will guide the development of highly efficient and tunable molecular platforms, enabling precise control over electrochemical processes and driving transformative breakthroughs across energy, catalysis, and materials science.