In the case of BT, a reversible one-electron reduction process was seen, this is in agreement with reports in the literature. In contrast, BT-MCAF with only one caffeine unit shows multiple redox processes. First, a non-reversible one-electron reduction is seen at -1.25 V (vs Fc + /Fc). This is followed by a twoelectron quasi-reversible reduction at E1/2 = -1.59 V vs Fc + /Fc (peak to peak separation ΔEp = 87 mV) and a third non-reversible one-electron reduction at -2.36 V (vs Fc + /Fc). During the anodic scan of BT-MCAF, an additional oxidation peak was seen at Ep = -0.98 V (vs Fc + /Fc). Consecutive CV scans of BT-MCAF confirmed the accumulation of this species near the electrode surface (Figure ). In the literature, similar oxidation peaks have been assigned to the oxidation of the dimerization product between two molecules of the radical anion of different small organic molecules. In the case of BT-MCAF, our experimental results suggest two reactive pathways (Figures ). The first pathway involves radical polymerization of BT-MCAF forming a film at the electrode surface (Figures ). The second reactive pathway involves the formation of a radical that can react with H2O, forming a hydroxylated derivative (Figures ). Although no dimer formation was observed for BT-MCAF in mass spectrometry measurements, the experimental results suggest that the incorporation of one caffeine unit as in BT-MCAF does not prevent other undesired side reactions. In contrast, the incorporation of two caffeine units as in BT-DCAF seems to play a role in the electrochemical stability of this latter molecule. The two caffeine units in BT-DCAF act as bulky substituents that block the access of radical species to the benzene ring of the BT structural core. This can be observed in the CV measurement of BT-DCAF. The electrochemical response is fully reversible and up to three electrons can be injected to BT-DCAF (Figure ). The first reversible one-electron reduction is seen at E1/2 = -1.38 V vs Fc + /Fc (ΔEp = 87 mV) and corresponds to the formation of a radical anion [BT-DCAF] •-. This is followed by a second one-electron reversible reduction at E1/2 = -1.93 V vs Fc + /Fc (ΔEp = 87 mV) corresponding to the formation of a dianion species [BT-DCAF] 2-. Finally, a third one-electron reduction at E1/2 = -2.36 V vs Fc + /Fc (ΔEp = 59 mV) was observed and corresponds to the formation of a radical trianion [BT-DCAF] •3-. This behavior is rather unique considering that most benzothiadiazole small organic molecules have been shown to reversible store a maximum of two electrons. 12,28-32 Multiple electron injection and the ability to store three electrons in a molecule it is highly relevant in the field of catalysis and can be exploited for special reactivities and enhanced stability. Additionally, no oxidation peaks were observed for BT-DCAF up to 1.0 V (vs Fc + /Fc) during the anodic scan of a CV measurement in CH2Cl2/MeCN (1:1) (Figure ). This suggests that neutral BT-DCAF is an electron deficient architecture and the removal of electrons from its highest occupied molecular orbital (HOMO) is thermodynamically unfavored. This is also a strong evidence supporting that there is no by-product such as dimerization during the cathodic scan.