Fig. 6: Experimental determination of reorganization energies of the ArCuPs using electrochemistry.
A CVs for 3SCC (red), 4SCC (blue), and the blank electrode (black) in 80 mM mixed buffer pH 6.5. Scan rate = 50 mV/s. The inset shows background corrected redox peaks. B RDE data for 0.25 mM 3SCC solutions at 295 K in 80 mM mixed buffer, 100 mM KCl at pH 6.5. Rotation rates = 250 rpm (black), 512 rpm (red), 850 rpm (blue), 1300 rpm (magenta), and 1850 rpm (olive). The inset shows the Koutecký-Levich (K-L) plots in the mass transport region used to obtain kET. The data are shown at potentials 0.017 V (black), 0.039 V (red), 0.062 V (blue), 0.084 V (magenta), and 0.108 V (olive). C Arrhenius plots were constructed using the kET obtained from the K-L analysis. D λT at different potentials obtained from the slopes of the Arrhenius plots. The dashed lines show the average λT. E ln(i) vs. t plots obtained from CA experiments. The slopes yield kapp (s-1) at a fixed η (data shown for η = 100 mV; see the SI for the remaining). F λCu-P measured from CA experiments at different η values. The dashed lines show the average λCu-P. The error bars represent SD from 2-3 independent sets of experiments. For CA experiments, 10 µL of 0.25 mM ArCuPs were dropped on PGE and dried under N2, and data were collected in 80 mM mixed buffer at pH 6.5. In C, D, and F, 3SCC is red, 4SCC is blue, and K6E/E8K-4SCC is orange.
