Efficient photosensitized splitting of the thymine dimer/oxetane unit on its modifying β-cyclodextrin by a binding electron donor

Abstract

Two modified β-cyclodextrins (β-CDs) with a thymine dimer and a thymine oxetane adduct respectively, TD-CD and Ox-CD, have been prepared, and utilized to bind an electron-rich chromophore, indole or N,N-dimethylaniline (DMA), to form a supramolecular complex. We have examined the photosensitized splitting of the dimer/oxetane unit in TD-CD/Ox-CD by indole or DMA via an electron-transfer pathway, and observed high splitting efficiencies of the dimer/oxetane unit. On the basis of measurements of fluorescence spectra and splitting quantum yields, it is suggested that the splitting reaction occurs in a supramolecular complex by an inclusion interaction between the modified β-CDs and DMA or indole. The back electron transfer, which leads low splitting efficiencies for the covalently-linked chromophore–dimer/oxetane compounds, is suppressed in the non-covalently-bound complex, and the mechanism has been discussed.