Figure 3: Supramolecular pKa shift of DAB‒CB[6] complex.

(a) 1H NMR titration curves for free ADA and ADA‒CB[6] complex by monitoring Hf proton (see Fig. 1) upon variations in pH in aqueous solutions at 25 °C, which revealed a different degree of protonation induced by the complexation of ADA with CB[6] ([ADA] = 0.5 mM and [CB[6]] = 1.0 mM); for the original data, see Supplementary Fig. S29; potentiometric fitting curve and pKa values calculation of (b) DAB and (c) DAB‒CB[6] system ([DAB] = 0.5 mM and [CB[6]] = 1.0 mM); (d) pH-dependent species distribution plot for the DAB‒CB[6] system. The distributions were obtained using the calculated pKa,1 and pKa,2 values. The H1DAB and H2DAB indicate the singly and doubly protonated species of DAB, respectively.