Modulation of Excited-State Proton Transfer of 2-(2′-Hydroxyphenyl)benzimidazole in a Macrocyclic Cucurbit[7]uril Host Cavity: Dual Emission Behavior and pK_a Shift

Graphical Abstract

Supramolecular dye encapsulation: The host–guest interaction between the prototropic forms of 2-(2′-hydroxyphenyl)benzimidazole and cucurbit[7]uril (see figure) leads to dual emission behavior as well as pK_a shifts in the ground and excited states due to the modulation of the proton-transfer behavior of the dye.

Abstract

The effect of the macrocyclic host, cucurbit[7]uril (CB7), on the photophysical properties of the 2-(2′-hydroxyphenyl)benzimidazole (HPBI) dye have been investigated in aqueous solution by using ground-state absorption and steady-state and time-resolved fluorescence measurements. All three prototropic forms of the dye (cationic, neutral, and anionic) form inclusion complexes with CB7, with the largest binding constant found for the cationic form (K≈2.4×10⁶ M⁻¹). At pH≈4, the appearance of a blue emission band upon excitation of the HPBI cation in the presence of CB7 indicates that encapsulation into the CB7 cavity retards the deprotonation process of the excited cation, and hence reduces its subsequent conversion to the keto form. Excitation of the neutral form (pH≈8.5), however, leads to an increase in the keto form fluorescence, indicating an enhanced excited-state intramolecular proton-transfer process for the encapsulated dye. In both the ground and excited states, the two pK_a values of the HPBI dye show upward shifts in the presence of CB7. The prototropic equilibrium of the CB7-complexed dye is represented by a six-state model, and the pH-dependent changes in the binding constants have been analyzed accordingly. It has been observed that the calculated pK_a values using this six-state model match well with the values obtained experimentally. The changes in the pK_a values in the presence of CB7 have been corroborated with the modulation of the proton-transfer process of the dye within the host cavity.