Electrochemical Behavior of Metal Complexes

The electrochemical behaviour of metal complexes encompasses the interconversion of oxidation states through electron‐transfer processes that are central to applications ranging from energy conversion to molecular sensing. Such redox events may be metal‐centred, ligand‐centred or involve metal–ligand cooperative mechanisms, and are governed by factors including ligand field strength, coordination geometry, electronic substituent effects and solvent environment. Experimental techniques such as cyclic voltammetry, spectroelectrochemistry and X‐ray photoelectron spectroscopy, often coupled with computational approaches such as density functional theory, provide complementary insights into the frontier molecular orbital structure, redox kinetics and thermodynamics. Understanding these processes enables the rational design of catalysts for water electrolysis and fuel cells, electrocatalysts for small‐molecule activation, and redox‐active materials for batteries and photoelectrochemical devices. Recent advances have focused on tuning redox potentials through ligand modification, elucidating multi‐electron transfer pathways and mapping reaction intermediates under operando conditions. This integrated experimental–theoretical framework continues to expand the global significance of metal complexes in sustainable energy technologies, biomedical imaging and chemical synthesis.

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Electrochemical Behavior of Metal Complexes publication trend

The graph below shows the total number of articles in electrochemical behavior of metal complexes across all publications each year (not limited to Nature Index journals).

Technical terms

Redox potential: The equilibrium potential at which a given oxidation–reduction reaction occurs at an electrode relative to a reference.

Cyclic voltammetry: An electroanalytical technique that sweeps the electrode potential and records current response to probe redox processes.

Spectroelectrochemistry: A method combining electrochemistry with spectroscopic detection to characterise redox‐induced species in real time.

EEC mechanism: A sequential electron‐transfer–electron‐transfer–chemical reaction pathway describing multi‐step redox processes.

Hammett constant: A numerical parameter quantifying the electron-donating or ‑withdrawing effect of substituents on aromatic systems.

References

1. Chemical and Electrochemical Investigation of the Oxidation of a Highly Reduced Fe6C Iron Carbide Carbonyl Cluster: A Synthetic Route to Heteroleptic Fe6C and Fe5C Clusters. Inorganic Chemistry (2025).
2. Electronic effect of substituent groups on the oxidation and reduction of bis(2,2′:6′,2″-terpyridine)ruthenium. Journal of Electroanalytical Chemistry (2023).
3. Redox Data of Tris(polypyridine)manganese(II) Complexes. Data (2022).