Cyclic voltammograms were recorded in bare TEMPO solutions with different molar equivalents of NOBF4 (0, 1.1 eq. and 2.4 eq.), as shown in Figure , to validate the hypothesis of TEMPO oxidation within the diazonium derivative (dC12TEMPONOBF4) obtained with excess NOBF4 (2.4 eq.). The analysis of the waves observed in the voltammograms recorded in the presence of NOBF4, acquired from the EOC towards positive and then negative potentials, indicates that only oxidized TEMPO species (TEMPO⁺) are present in equilibrium with NOBF4 (Figure , blue lines). Notably, EOC values shifted towards positive potentials with increasing molar equivalents of NOBF4, signifying an evident transition from radical to oxidized species. Exceeding stoichiometry with 2.4 equivalents of NOBF4 reduced the reversibility of the TEMPO/TEMPO⁺ redox system, as shown by the increased reduction current and the diffusional plateau intensity, resembling catalytic processes. This irreversibility is attributed to excess NOBF4 oxidizing regenerated TEMPO radicals. This phenomenon was reproduced using the KISSA electrochemical simulator, which simulated TEMPO's behavior with 1.1 and 2.4 equivalents of NOBF4, following the outlined mechanism (Figure ):