Excited-state proton transfer in confined medium. 4-methyl-7-hydroxyflavylium and ß-naphthol incorporated in cucurbit[7]uril.

ABSTRACT

Excited-state proton transfer (ESPT) was studied by fluorescent emission using a mathematical model recast from the Weller theory. The titration curves can be fitted with three parameters pK(a) (acidity constant of the ground sate), pK(ap)* (apparent acidity constant of the excited state), and η(A*), the efficiency of excited base formation from the excited acid. ß-Naphthol and 4-metyhl-7-hydroxyflavylium were studied in aqueous solution and upon incorporation in cucurbit[7]uril. For all the compounds studied the interaction with the host leads to 11 adducts and the ground-state pK(a) increases upon incorporation. Whereas the ESPT of 4-methyl-7-hydroxyflavylium practically does not change in the presence of the host, in the case of ß-naphthol it is prevented and the fluorescence emission titration curves are coincident with those taken by absorption. The position of the guest inside the host was investigated by NMR experiments and seems to determine the efficiency of the ESPT. The ESPT decreases for the guest, exhibiting a great protection of the phenol to the bulk water interaction.