Recent Advances in Synthesis, Characterization, and Electrochemical Investigations of Manganese Derived Complexes

ABSTRACT Manganese‐based complexes continue to attract sustained interest owing to their rich redox chemistry, earth abundance, and central roles in catalysis and biological systems. This review provides a comprehensive account of progress made in the field over the last decade (2016–2026), with a particular focus on the rational design and synthesis of manganese complexes spanning Mn II , Mn III , and Mn IV oxidation states. We examine a diverse array of macrocyclic platforms, providing a comparative analysis of how specific architectures including triazamacrocycles, tetraazamacrocycles (such as cyclen‐type, pyclen‐type, and diazepane‐based complexes), and pentaazamacrocyclic systems dictate coordination geometry and metal–ligand covalency. The discussion further explores the utility of Robson‐type macrocyclic ligands, cross‐bridged frameworks, and miscellaneous hybrid organic–inorganic architectures in stabilizing diverse redox states. While centering on structural characterization and electrochemical investigation, the review balances these insights with the synthetic strategies required to access higher‐valent species. Specific attention is devoted to how ligand topology and secondary coordination sphere effects govern specific catalysis and electrocatalysis, including water oxidation and oxygen reduction reactions. By integrating synthetic methodology with redox behavior and magnetic insights, this review highlights emerging design principles for manganese‐based systems and outlines future directions for sustainable, bioinspired chemistry.