In this work, four derivatives of the pentaazamacrocyclic Mn‐pyane [pyane = trans‐2,13‐dimethyl‐3,6,9,12,18‐pentaazabicyclo[12.3.1]‐octadeca‐1(18),14,16‐triene] complex were synthesized and characterized, carrying small substituents at the pyridine ring that allow fine‐tuning of the manganese centered redox potential, without significant change to the overall complex arrangement that is crucial for a correct comparison regarding their superoxide dismutase mimetic (SODm) capabilities. The crystal structure of the seven‐coordinate OMe‐substituted Mn‐pyane complex was obtained. The synthesized complexes will serve for future investigations related to an effect of complex redox potentials on their mechanistic behavior within SOD catalysis.